HUE029187T2 - Use of a surface-treated calcium carbonate in water purification and for the dewatering of sludges and sediments and resulting composite material - Google Patents

Use of a surface-treated calcium carbonate in water purification and for the dewatering of sludges and sediments and resulting composite material Download PDF

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Publication number
HUE029187T2
HUE029187T2 HUE12778745A HUE12778745A HUE029187T2 HU E029187 T2 HUE029187 T2 HU E029187T2 HU E12778745 A HUE12778745 A HU E12778745A HU E12778745 A HUE12778745 A HU E12778745A HU E029187 T2 HUE029187 T2 HU E029187T2
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Hungary
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calcium carbonate
sludge
water
treated
μίτι
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HUE12778745A
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Hungarian (hu)
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Daniel E Gerard
Hans-Georg Hartan
Joachim Schoelkopf
Michael Skovby
Patrick A C Gane
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Omya Int Ag
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041Oxides or hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268Macromolecular compounds
    • B01J20/327Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268Macromolecular compounds
    • B01J20/3276Copolymers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/148Combined use of inorganic and organic substances, being added in the same treatment step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007Contaminated open waterways, rivers, lakes or ponds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Treatment Of Sludge (AREA)
  • Removal Of Specific Substances (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Description

Description [0001] The invention relates to the use of a surface-treated calcium carbonate for water purification and/or dewatering of sludges and/or sediments, as well as to a composite material comprising a surface-treated calcium carbonate and impurities originated from different sources obtainable by said use.
[0002] Water pollution has posed a serious problem all over the world. In this regard, water pollution is suggested as being the leading cause of death and diseases in developing countries but also industrialized countries continue struggling with such pollution problems. In general, water, sludges and sediments are referred to as being polluted when impaired by anthropogenic contaminants and either does not support a human use, such as serving as drinking water, and/or has negative impacts on aquatic and/or land based flora and fauna.
[0003] The specific contaminants or impurities leading to pollution in water, sludges and sediments, include a wide variety of chemical substances, pathogens and physical or sensory changes such as elevated temperature and discoloration. In this regard, the chemical contaminants may include organic substances as well as inorganic substances. In particular, many of the inorganic components may also be naturally occurring (calcium salts, sodium salts, manganese salts etc.) so that their concentration is often the key in determining what is a natural water, sludge, or sediment component and what is a contaminant. Sources of such water, sludge or sediment pollutions typically originate from urban waste waters, i.e. domestic waste water or a mixture of domestic waste water with industrial waste water and/or run-off rain water, as well industrial waste waters, i.e. any waste water which is discharged from premises used for carrying on any trade or industry.
[0004] In the art, several approaches for the purification of polluted water, sludges or sediments have been proposed. For instance, one approach involves the addition offlocculants to remove or at least to reduce the amount of contaminants such as fine solids, micro-organisms and dissolved inorganic and organic materials. Flocculation refers to a process where dissolved compounds and/or colloidal particles are removed from the solution in the form of floes or "flakes." The term is also used to refer to the process by which fine particulates are caused to clump together into floes. The floes may then float to the top of the liquid, settle to the bottom of the liquid, or can be readily filtered from the liquid.
[0005] Flocculants, or flocculating agents, are chemicals that are used to promote flocculation. Flocculants are used in water treatment processes to improve the sedimentation or filterability of small particles. Many flocculants are multivalent cations such as aluminium, iron, calcium or magnesium. These positively charged ions interact with negatively charged particles and molecules to reduce the barriers to aggregation. In addition, many of these chemicals, under appropriate pH and other conditions, react with water to form insoluble hydroxides which, upon precipitating, linktogether to form long chains or meshes, physically trapping small particles into the larger floe.
[0006] Common flocculants or coagulants used are aluminium sulphate or polyaluminium chloride (PAC). Aluminium sulphate reacts with water to form floes of aluminium hydroxide. Coagulation with aluminum compounds may leave a residue of aluminium in the finished water, which can be toxic to humans at high concentrations. In solutions of polyaluminium chloride (PAC), aluminium ions have formed into polymers consisting of clusters of ions bridged by oxygen atoms. PAC is used e.g. for the treatment of brown drinking water comprising organic materials such as leaves and/or inorganic materials such as iron and manganese compounds which cause the brown discolouration. Flowever, PAC is generally not sufficient to remove all brown discolouration from the water.
[0007] Iron(lll) chloride is another common coagulant. Iron(lll) coagulants work over a larger pH range than aluminium sulphate but are not effective with many source waters. Coagulation with iron compounds typically leaves a residue of iron in the finished water. This may impart a slight taste to the water, and may cause brownish stains on porcelain fixtures. Furthermore, iron(lll) chloride impart corrosion risks in the water treatment system.
[0008] Further well-known flocculants for the water treatment based on a high specific surface area such as activated carbon or bentonite have the general drawback that they are very difficult to separate after the adsorption of the substance to be removed from the medium due to their finely divided state.
[0009] EP0273335 and CA2734310 disclose the use of a calcium carbonate that has been coated with a cationic polymer for the purification of water. The skilled man also knows US 2006/0273039 A1, which refers to a product and an apparatus for cleaning water or industrial and sewage waste water includes a mixture of diatomite that is heated and stirred to impart an enhanced negative electrical charge to the diatomite. EP 2 0111 766 A1 relates to a process for reducing the amount of organic components in water, wherein a surface-reacted natural calcium carbonate and a hydrophobic adsorbent, selected from the group consisting of talc, hydrophobised calcium carbonate, hydrophobised bentonite, hydrophobised kaolinite, hydrophobised glass, or any mixture thereof, are brought into contact with the water to be purified, the surface-reacted natural calcium carbonate being the reaction product of a natural calcium carbonate with an acid and carbon dioxide, which is formed in situ by the acid treatment and/or supplied externally, and the surface-reacted natural calcium carbonate being prepared as an aqueous suspension having a pH of greater than 6.0, measured at 20 °C. EP 1 982 759 A1 relates to a process for the purification of water, wherein a surface-reacted natural calcium carbonate is brought into contact with the water to be purified, the surface-reacted natural calcium carbonate being the reaction product of a natural calcium carbonate with an acid and carbon dioxide, which is formed in situ by the acid treatment and/or supplied externally. EP 1 974 807 A1 relates to the removal of endocrine disrupting compounds from an aqueous medium by adding surface-reacted natural calcium carbonate or an aqueous suspension comprising surface-reacted calcium carbonate and having a pH greater than 6.0 measured at 20 °C, to the medium, wherein the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate with carbon dioxide and one or more acids. EP 1 974 806 A1 relates to a process for the purification of water by adding surface-reacted natural calcium carbonate or an aqueous suspension comprising surface-reacted calcium carbonate and having a pH greater than 6.0 measured at 20 °C, to the medium, wherein the surface-reacted calcium carbonate is a reaction product of natural calcium carbonate with carbon dioxide and one or more acids. EP 1 493 716 A1 refers to a wastewater treatment process, wherein wastewater containing fluoride ion and/or phosphate ion is added with a calcium-containing compound, and then added with a filmforming agent and complexion agent.
[0010] One problem with the addition of such flocculants, however, is that it tends to merely bind and agglomerate organic contaminants while inorganic impurities are still finely dispersed in the water sample. Furthermore, the flocculated material needs to be removed from the water phase by a dewatering process such as filtration or centrifugation so that the obtained filter cake can be further disposed by e.g. burning. However, due to the overall incomplete flocculation process the water content in such obtained filter cake is comparatively high resulting in a dramatically increased energy consumption on combustion.
[0011] Another strategy involves the use of polymeric flocculation aids in conjunction with other inorganic flocculants. However, when used in combination with one of the above-mentioned inorganic flocculants such as iron(lll) chloride, the polymeric flocculation aid needs to be cationic, i.e. needs to have a positive overall charge, for effectively acting as a flocculation aid. The long chains of positively charged polymers can help to strengthen the floe making it larger, faster settling and easier to filter out. Due to the restriction to cationic polymers, the process flexibility is reduced.
[0012] A known polymeric flocculation aid is polyacrylamide. By using of specific comonomers, anionic as well as cationic, polyacrylamide can be provided. However, as already indicated above, when used in combination with inorganic flocculants such as iron(lll) chloride, only cationic polyacrylamide is effective.
[0013] However, one problem with this approach is that these polymeric flocculation aids are usually overdosed to a large extent in order to ensure the agglomeration of all fine solid particles in the water to be treated. Thus, after the separation of the flocculated material from the water phase, the content of polyacrylamide in the filtrate is usually increased due to the high amounts of polymeric flocculating aids used. However, as there are severe environmental concerns regarding water containing polymeric flocculation aids, and especially polyacrylamide, the filtrate cannot be readily disposed in nature and, thus, further time and cost consuming purification steps are required to remove the polymeric flocculation aid from the filtrate.
[0014] Therefore, there is a continuous need for alternative water treatment processes, which provide a better performance than existing processes and effectively decrease the concentration of impurities and especially inorganic impurities and the concentration of polymeric flocculation aids in waste water to be treated but still enables easy performance at low cost.
[0015] This and other objects are solved by the subject-matter of the present invention. A process for the purification of water and/or dewatering of sludges and/or sediments, relevant for the present invention, comprises the following steps of: a) providing water to be purified and/or sludge and/or sediment to be dewatered comprising impurities; b) providing at least one surface-treated calcium carbonate, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer, and c) contacting the water and/or sludge and/or sediment of step a) with the at least one surface-treated calcium carbonate of step b) for obtaining a composite material of surface-treated calcium carbonate and impurities.
[0016] The inventors surprisingly found that the foregoing process leads to an improved quality of the obtained filter cake and purified water providing a lower amount of polymeric flocculation aids than water, sludges and/or sediments treated the same way but without contacting it with the at least one surface-treated calcium carbonate (step c)). More precisely, the inventors found that the quality of water and of a filter cake being obtained by a purification process can be improved by a defined calcium carbonate that is surface-treated with cationic polymers.
[0017] It should be understood that for the purposes of the present invention, the following terms have the following meaning:
The term "purification" in the meaning of the present invention refers to the removal of harmful compounds and/or other compounds not tolerated in the water.
[0018] Furthermore, the term refers to the reduction in concentration of naturally occurring compounds in the water.
[0019] The term "dewatering" in the meaning of the present invention refers to the removal of residual liquid from sludges and/or sediments.
[0020] The term " impurities" in the meaning of the present invention refers to naturally occurring compounds, wherein their concentration in the water and/or sludge and/or sediment is above the natural concentration and/or compounds that are not naturally occurring.
[0021] The term "calcium carbonate" in the meaning of the present invention refers to surface modified calcium carbonate (MCC). "Ground calcium carbonate" (GCC) is a calcium carbonate obtained from natural sources, such as limestone, marble or chalk or dolomite, and processed through a treatment such as grinding, screening and/orfractionizing by a wet and/or dry process, for example, by means of a cyclone or classifier. "Precipitated calcium carbonate" (PCC) is a synthesized material, generally obtained by precipitation following reaction of carbon dioxide and lime in an aqueous environment or by precipitation of a calcium and carbonate ion source in water. "Surface-modified calcium carbonate" (MCC) in the meaning of the present invention refers to a natural calcium carbonate and/or precipitated calcium carbonate obtained by reacting it with an acid or ion and with carbon dioxide prior to the preparation of the surface-treated calcium carbonate, wherein the carbon dioxide is formed in situ by the acid treatment and/or is supplied from an external source.
[0022] The term "surface-treated" calcium carbonate in the meaning of the present invention refers to a ground calcium carbonate and/or precipitated calcium carbonate and/or surface-modified calcium carbonate that has been processed with cationic polymers through an additional treatment step in order to render the surface of the calcium carbonate particles more cationic.
[0023] The term "cationic polymer" in the meaning of the present invention refers to any polymer providing for a positive overall charge when bound to calcium carbonate particles. Thus, the presence of anionic monomer units is not excluded as long as there are still sufficient cationic monomer units providing a positive overall charge. The same applies for amphotheric polymers which provide for an overall positive charge when bound to the calcium carbonate particles.
[0024] The term "accessible surface area" in the meaning of the present invention refers to the surface of the calcium carbonate particle that is accessible or exposed to the cationic polymer applied by mixing and/or coating techniques known to the skilled person and therebyforming a monolayer of cationic polymeron the surface of the calcium carbonate particle. In this regard, it should be noted that the amount of cationic polymer required for full saturation of the accessible surface area is defined as a monolayer concentration. Higher concentrations thus can be chosen thereby forming bilayered or multi-layered structures on the surface of the calcium carbonate particle. Such monolayer concentrations can be readily calculated by the skilled person, based on the publication of Papirer, Schultz and Turchi (Eur. Polym. J., Vol. 20, No. 12, pp. 1155-1158, 1984).
[0025] An aspect of the present invention is directed to the use of a surface-treated calcium carbonate for water purification and/or dewatering of sludges and/or sediments, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer. A further aspect of the present invention is directed to the use of a surface-treated calcium carbonate for reducing the amount of polymeric flocculation aids in water and/or sludges and/or sediments, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer.
[0026] The surface-treated calcium carbonate comprises surface-modified calcium carbonate.
[0027] It is further preferred that the calcium carbonate particles of the surface-treated calcium carbonate have a weight median particle diameter d5Q value of between 0.04 μηι and 250 μίτι, preferably between 0.06 μηι and 225 μίτι, more preferably between 1 μίτι and 200 μίτι, even more preferably between 1 μίτι and 150 μίτι, and most preferably between 1 μίτι and 100 μίτι and/or the calcium carbonate particles of the surface-treated calcium carbonate have a specific surface area of from 1 to 250 m2/g, more preferably from 20 to 200 m2/g, even more preferably from 30 to 150 m2/g and most preferably from 30 to 100 m2/g. It is still further preferred that the coating of the surface-treated calcium carbonate comprises at least one cationic polymer having a positive charge density in the range of 1 mEq/g and 15 mEq/g, more preferably in the range of 2.5 mEq/g and 12.5 mEq/g and most preferably in the range of 5 mEq/g and 10 mEq/g and/or the coating of the surface-treated calcium carbonate comprises at least one cationic polymer in which at least 60 % of the monomer units have a cationic charge, preferably at least 70 %, more preferably at least 80 %, even more preferably at least 90 % and most preferably equal to 100 %. It is even further preferred that the coating of the surface-treated calcium carbonate comprises at least one cationic polymer having a weight average molecular weight Mw of below 1,000,000 g/mole, more preferably from 50,000 to 750,000 g/mole, even more preferably from 50,000 to 650,000 g/mole and most preferably from 100,000 to 300,000 g/mole. It is also preferred that the coating of the surface-treated calcium carbonate comprises at least one cationic polymer being a homopolymer based on monomer units selected from the group consisting of diallyldialkyl ammonium salts; tertiary and quaternized amines; quaternized imines; and most preferably diallyldimethyl ammonium chloride. It is also preferred that the coating of the surface-treated calcium carbonate comprises at least one cationic polymer being a copolymer based on monomer units selected from diallyldialkyl ammonium salts and comonomer units selected from the group consisting of acrylamide; methacrylamide; N,N-dimethyl acrylamide; acrylic acid; methacrylic acid; vinylsulfonic acid; vinyl pyrrolidone; hydroxyl ethyl acrylate; styrene; methyl methacrylate; vinyl acetate and mixtures thereof, preferably the monomer units are selected from diallyldialkyl ammonium salts and comonomer units selected from acrylamide and acrylic acid. It is further preferred that at least 10 % of the accessible surface area of the calcium carbonate is covered by a coating comprising a cationic polymer, preferably at least 20 % of the accessible surface area, more preferably at least 30 %, even more preferably at least 40 % and most preferably at least 50 % of the accessible surface area. It is still further preferred that the surface-treated calcium carbonate is in powder form and/or in the form of granules or in the form of slurry. In a further embodiment the surface-treated calcium carbonate is used in combination with at least one polymeric flocculation aid. The polymeric flocculation aid has a weight average molecular weight Mw in the range from 100,000 to 10,000,000 g/mole, preferably in the range from 300,000 to 5,000,000 g/mole, more preferably in the range from 300,000 to 1,000,000 g/mole and most preferably in the range from 300,000 to 800,000 g/mole and/or the polymeric flocculation aid is non-ionic or ionic, preferbly a cationic or anionic polymer selected from polyacrylamides, polyacrylates, poly(diallyldimethylammonium chloride), polyethyle-neimines, polyamines, starches and mixtures thereof.
[0028] A further aspect of the present invention is directed to a composite material comprising a surface-treated calcium carbonate and impurities obtainable by the process.
[0029] When in the following reference is made to preferred embodiments or technical details of the relevant process for the purification of water and/or dewatering of sludges and/or sediments, it is to be understood that these preferred embodiments or technical details also refer to the inventive use of the surface-treated calcium carbonate for water purification and/or dewatering of sludges and/or sediments, to the inventive use of the surface-treated calcium carbonate for reducing the amount of polymeric flocculation aids in water and/or sludges and/or sediments as well as to the composite material comprising the surface-treated calcium carbonate and impurities defined herein and vice versa (as far as applicable).
[0030] According to one preferred embodiment of the process, the water and/or sludge and/or sediment of step a) is selected from industrial waste water, drinking water, urban waste water, sludge such as harbour sludge, river sludge, coastal sludge or digested sludge, waste water or process water from breweries or other beverage industries, waste water or process water in the paper industry, colour-, paints-, or coatings industry, agricultural waste water, slaughterhouse waste water, leather industry waste water and leather tanning industry.
[0031] According to one preferred embodiment of the inventive process, the calcium carbonate particles of the at least one surface-treated calcium carbonate have a weight median particle diameter d50 value of between 0.01 μΜ and 250 μίτι, preferably between 0.06 μίτι and 225 μίτι, more preferably between 1 μίτι and 200 μίτι, even more preferably between 1 μίτι and 150 μίτι and most preferably between 1 μίτι and 100 μίτι and/or the calcium carbonate particles of the at least one surface-treated calcium carbonate have a specific surface area of from 1 to 250 m2/g, more preferably from 10 to 200 m2/g, even more preferably from 20 to 150 m2/g and most preferably from 30 to 100 m2/g.
[0032] According to another preferred embodiment of the inventive process, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer having a positive charge density in the range of 1 mEq/g and 15 mEq/g, more preferably in the range of 2.5 mEq/g and 12.5 mEq/g and most preferably in the range of 5 mEq/g and 10 mEq/g and/or the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer in which at least 60 % of the monomer units have a cationic charge, preferably at least 70 %, more preferably at least 80 %, even more preferably at least 90 % and most preferably equal to 100 %.
[0033] According to yet another preferred embodiment of the inventive process, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer having a weight average molecular weight Mw of below 1,000,000 g/mole, more preferably from 50,000 to 750,000 g/mole, even more preferably from 50,000 to 650,000 g/mole and most preferably from 100,000 to 300,000 g/mole.
[0034] According to one preferred embodiment of the inventive process, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer being a homopolymer based on monomer units selected from the group consisting of diallyldialkyl ammonium salts; tertiary and quaternized amines; quaternized imines; preferably diallyldialkyl ammonium salts and most preferably diallyldimethyl ammonium chloride.
[0035] According to another preferred embodiment of the process, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer being a copolymer based on monomer units selected from diallyldialkyl ammonium salts and comonomer units selected from the group consisting of acrylamide; methacrylamide; Ν,Ν-dimethyl acrylamide; acrylic acid; methacrylic acid; vinylsulfonic acid; vinyl pyrrolidone; hydroxyl ethyl acrylate; styrene; methyl methacrylate; vinyl acetate and mixtures thereof, preferably the monomer units are selected from diallyldialkyl ammonium salts and comonomer units selected from acrylamide and acrylic acid.
[0036] According to yet another preferred embodiment of the process, at least 10 % of the accessible surface area of the calcium carbonate is covered by a coating comprising a cationic polymer, preferably at least 20 % of the accessible surface area, more preferably at least 30 %, even more preferably at least 40 % and most preferably at least 50 % of the accessible surface area.
[0037] According to one preferred embodiment of the process, the at least one surface-treated calcium carbonate is in powder form and/or in the form of granules or in the form of slurry.
[0038] According to another preferred embodiment of the process, the process further comprises step d) of contacting the water and/or sludge and/or sediment to be purified of step a) with at least one polymeric flocculation aid. It is preferred that the polymeric flocculation aid has a weight average molecular weight Mw in the range from 100,000 to 10,000,000 g/mole, preferably in the range from 300,000 to 5,000,000 g/mole, more preferably in the range from 300,000 to 1,000,000 g/mole and most preferably in the range from 300,000 to 800,000 g/mole and/or the polymeric flocculation aid is nonionic or ionic, preferbly a cationic or anionic polymer selected from polyacrylamides, polyacrylates, poly(diallyldimethy-lammonium chloride), polyethyleneimines, polyamines, starches and mixtures thereof [0039] According to yet another preferred embodiment of the process, step c) and stepd) are carried out simultaneously or separately, preferably separately.
[0040] According to one preferred embodiment of the process, step c) and/or step d) are carried out by at least partially covering the surface of the water and/or sludge and/or sediment to be treated of step a) with the at least one surface-treated calcium carbonate of step b) and/or mixing the water and/or sludge and/or sediment to be treated of step a) with the at least one surface-treated calcium carbonate of step b).
[0041] According to another preferred embodiment of the process, step c) and/orstep d) are repeated one or more times.
[0042] According to yet another preferred embodiment of the process, the composite material of the at least one surface-treated calcium carbonate and impurities is removed from the water and/or sludge and/or sediment phase by filtration, sedimentation and/or centrifugation.
[0043] According to one preferred embodiment of the process, the water and/or sludge and/or sediment obtained by the process contains an amount of polymeric flocculation aid of at least 10 wt.-%, preferably at least 20 wt.-%, more preferably at least 30 wt.-%, even more preferably at least 40 wt.-%, still more preferably at least 50 wt.-% and most preferably at least 60 wt.-% below the amount of polymeric flocculation aid contained in a corresponding water and/or sludge and/or sediment being treated the same way but in the absence of the at least one surface-treated calcium carbonate.
[0044] As set out above, the process for the purification of water and/or dewatering of sludges and/or sediments comprises the steps a), b) and c). In the following, it is referred to further details of the present invention and especially the foregoing steps of the process for the purification of water providing improved filter cake and water quality in that the amount of polymeric flocculation aids is reduced.
Step a): provision of water and/or sludge and/or sediment to be purified [0045] According to step a) of the process, water to be purified and/or sludge and/or sediment to be dewatered is provided, wherein the water and/or sludge and/or sediment comprises impurities.
[0046] The water and/or sludge and/or sediment treated by the process is preferably selected from industrial waste water, drinking water, urban waste water, sludge such as harbour sludge, river sludge or digested sludge, waste water or process water from breweries or other beverage industries, waste water or process water in the paper industry, colour-, paints-, or coatings industry, agricultural waste water, slaughterhouse waste water, leather industry waste water and leather tanning industry.
[0047] Within the context of the present invention, the term "process water" refers to any water which is necessary to run or maintain an industrial process. The term "waste water" refers to any water drained from its place of use, e.g. an industrial plant.
[0048] The term "sludge" in the meaning of the present invention refers to any kind of sludge, e.g. primary sludge, biological sludge, mixed sludge, digested sludge, physico-chemical sludge and mineral sludge. In this regard, primary sludge comes from the settling process and usually comprises large and/or dense particles. Biological sludge comes from the biological treatment of wastewater and is usually made of a mixture of microorganisms. These microorganisms, mainly bacteria, amalgamate in bacterial floes through the synthesis of exo-polymers. Mixed sludge is a blend of primary and biological sludges and usually comprises 35 wt.-% to 45 wt.-% of primary sludge and 65 wt.-% to 55 wt.-% of biological sludge. Digested sludge comes from a biological stabilizing step in the process called digestion and is usually performed on biological or mixed sludge. It can be done under different temperatures (mesophilic or thermophilic) and with orwithoutthe presence of oxygen (aerobic oranaerobic). Physico-chemical sludge is the result of a physico-chemical treatment of the wastewater and is composed of floes produced by the chemical treatment. Mineral sludge is given to sludge produced during mineral processes such as quarries or mining beneficiation processes and essentially comprises mineral particles of various sizes).
[0049] Within the context of the present invention, the term "sediment" refers to any water containing particles of naturally occurring material.
[0050] Preferably, the water and/or sludge and/or sediment to be treated comprises organic impurities and/or inorganic impurities.
[0051] In accordance with the process, the water and/or sludge and/or sediment to be treated comprise inorganic impurities. The term "inorganic impurities" in the meaning of the present invention refers to naturally occurring compounds, wherein their concentration in the water and/or sludge and/or sediment is above the natural concentration typically observed in water and/or compounds that are not naturally occurring.
[0052] In particular, many inorganic impurities are typically present as dissolved inorganics, i.e. inorganic substances in solution, such as bicarbonates of calcium and/or magnesium, which give rise to temporary hardness, while the sulfates and chlorides cause permanent hardness. Other inorganic impurities present in water and/or sludge and/or sediment include carbon dioxide, which dissolves in water to give weakly acidic carbonic acid, sodium salts, silicates leached from sandy river beds, chlorides from saline intrusion, aluminium from dosing chemicals and minerals, phosphates from fertilizers, fluoride compounds derived from additives promoting strong teeth and as discharge from fertilizer and aluminum factories, nitrate and nitrite compounds derived as runoff from fertilizer use as well as leaking from septic tanks, sewage or chlorine derived from the chlorination of the municipal system to combat water-borne diseases and cyanide compounds derived as discharge from steel and metal factories as well as plastic and fertilizer factories.
[0053] If the water and/or sludge and/or sediments to be treated comprises heavy metal impurities, they are typically ferrous and ferric iron compounds derived from minerals and rusty iron pipes; antimony compounds derived as discharge from petroleum refineries, fire retardants or electronics; arsenic compounds derived from erosion of natural deposits, runoff from orchards, runoff from glass and electronics production wastes; barium compounds as discharge of drilling wastes and from metal refineries; beryllium compounds derived as discharge from metal refineries and coal-burning factories as well as electrical, aerospace, and defense industries; cadmium compounds derived from corrosion processes of galvanized pipes, discharge from metal refineries and runoff from waste batteries and paints; chromium compounds derived from discharge from steel and pulp mills; cobalt and nickel compounds derived as discharge from metal refineries and runoff from waste batteries; copper and lead compounds derived from corrosion processes of household plumbing systems;; selenium compounds derived as discharge from petroleum refineries and mines such as mines for metal or metal ore extraction or any other mines producing polluted sludge; thallium compounds derived as leaching from ore-processing sites as well as discharge from electronics, glass, and drug factories or zinc, or mercury compounds derived from mining, smelting metals (like zinc, lead and cadmium) and steel production, as well as burning coal and certain wastes can release zinc into the environment.
[0054] Furthermore, the water and/or sludge and/or sediment to be treated may also comprise organic impurities. In the context of the present invention, the term "organic impurities" has to be interpreted broadly and encompasses specific organic compounds such as surfactants, polycyclic compounds, cholesterol, or endocrine disrupting compounds as well as more complex organic materials (e.g. organic material from microorganisms).
[0055] Impurities within the meaning of the present invention shall encompass organic, inorganic, biological, mineral impurities or combinations thereof, wherein said impurities can be present in dissolved, dispersed, or emulsified forms as well as in colloidal form or adsorbed to solids, as well as in combination thereof, or still other forms.
[0056] Preferably, the water and/or sludge and/or sediment to be purified includes at least one of the following organic impurities which are selected from the group consisting of surfactants; cholesterol; endocrine disrupting compounds; amino acids; proteins; carbohydrates; defoamers; sizing agents selected from the group consisting of alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), or mixtures thereof; polyvinylacetates; polyacrylates, in particular polyacrylate latex; styrene butadiene copolymers, in particular styrene butadiene latex; microorganisms; mineral oils; vegetable oils and fats; or any mixture thereof.
[0057] In another preferred embodiment of the process, the organic impurities also comprise pitch. The term "pitch" as used in the present invention refers to a specific type of organic material generated in the papermaking or pulping process. The primary fibre source in papermaking is wood, which is reduced to its constituent fibres during pulping by combinations of grinding, thermal and chemical treatment. During this process the natural resin contained within the wood is released into the process water in the form of microscopic droplets. These droplets are referred to as pitch. The chemical composition of pitch is generally divided into four classes of lipophilic components: fats and fatty acids; steryl esters and sterols; terpenoids; and waxes. The chemical composition depends on the fibre source, such as variety of tree, and on the seasonal growth from which the sample is produced.
[0058] If the organic component is a surfactant, the surfactant can be ionic or non-ionic. If the surfactant is anionic, it can have a functional group selected from carboxylate, sulfate, or sulfonate. If the surfactant is cationic, its functional group can be a quaternary ammonium group.
[0059] If the water and/or sludge and/or sediment to be treated comprises endocrine disrupting compounds, they are preferably selected from the group comprising, e.g. endogenous hormones such as 17ß-estradiol (E2), estrone (E1), estriol (E3), testosterone or dihydro testosterone; phyto and myco hormones such as ß -sitosterol, genistein, daidzein orzeraleon; drugs such as 17 ß -ethinylestradiol (EE2), mestranol (ME), diethylstilbestrol (DES), and industrial chemicals such as 4-nonyl phenol (NP), 4-tert-octyl phenol (OP), bisphenol A (BPA), tributyltin (TBT), methylmercury, phthalates, PAK or PCB.
[0060] If the water and/or sludge and/or sediment to be treated comprises defoamer, it can be ethylene oxide glycol ether, a silicone oil based defoamer, a fatty acid ester defoamer, or any mixture thereof. The defoamer may be preferably selected from stickies. Stickies are potentially deposit-forming components originating from recycled paper. In general, examples are glues, hot-melt plastics, printing inks, and latex. The papermaking industry utilizes various amounts of recycled fiber or papers as a source of paper fiber furnish in the production of finished paper products. The recycled papers are often contaminated with the synthetic polymeric materials outlined above and these polymeric materials are referred to as stickies in the papermaking art. Stickies are different from pitch which is a naturally occurring resinous material from the extractive fraction of wood. Reference is made to E.L. Back and L.H. Allen, "Pitch Control, Wood Resin and Deresination", Tappi Press, Atlanta, 2000, wherein stickies are described in further detail.
[0061] If the water and/or sludge and/or sediment to be treated comprises microorganisms, they are preferably selected from bacteria, fungi, archaea or protists.
[0062] Preferred vegetable oils are edible oils such as coconut oil, corn oil, cottonseed oil, canola oil, palm oil, soybean oil, sunflower oil, or linseed oil.
[0063] The exact composition of the water and/or sludge and/or sediment to be purified and especially the amount of inorganic and/or organic impurities varies depending on the origin of the polluted water and/or sludge and/or sediment.
Step b): provision of at least one surface-treated calcium carbonate [0064] According to step b) of the process, at least one surface-treated calcium carbonate is provided.
[0065] In accordance with the process, at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer.
[0066] The surface-treated calcium carbonate comprises surface-modified calcium carbonate (MCC).
[0067] Alternatively, the surface-treated calcium carbonate comprises a mixture of GCC (ground or natural calcium carbonate) and MCC. Alternatively, the surface-treated calcium carbonate comprises a mixture of PCC (precipitated or synthetic calcium carbonate) and MCC.
[0068] In all embodiments, the surface-treated calcium carbonate comprises surface-modified calcium carbonate (MCC).
[0069] Ground (or natural) calcium carbonate (GCC) is understood to be a naturally occurring form of calcium carbonate, mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble rocks. Calcium carbonate is known to exist as three types of crystal polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystal polymorph, is considered to be the most stable crystal form of calcium carbonate. Less common is aragonite, which has a discrete or clustered needle orthorhombic crystal structure. Vaterite is the rarest calcium carbonate polymorph and is generally unstable. Ground calcium carbonate is almost exclusively of the calcitic polymorph, which is said to be trigonal-rhombohedral and represents the most stable of the calcium carbonate polymorphs.
[0070] Preferably, the source of the ground calcium carbonate is selected from the group comprising marble, chalk, calcite, dolomite, limestone and mixtures thereof. In a preferred embodiment, the source of the ground calcium carbonate is calcite.
[0071] The term "source" of the calcium carbonate in the meaning of the present invention refers to the naturally occurring mineral material from which the calcium carbonate is obtained. The source of the calcium carbonate may comprise further naturally occurring components such as magnesium carbonate, alumino silicate etc.
[0072] Additionally or alternatively, the surface-treated calcium carbonate comprises a precipitated calcium carbonate (PCC). Calcium carbonate polymorphs of the PCC type often include, in addition to calcites, less stable polymorphs of the aragonitic-type, which has an orthorhombic, acicular crystal shape, and hexagonal vateritic-type, which has an even lower stability than aragonite. The different PCC forms may be identified according to their characteristic x-ray powder diffraction (XRD) peaks. PCC synthesis most commonly occurs by a synthetic precipitation reaction that includes a step of contacting carbon dioxide with a solution of calcium hydroxide, the latter being most often provided on forming an aqueous suspension of calcium oxide, also known as burnt lime, and the suspension of which is commonly known as milk of lime. Depending on the reaction conditions, this PCC can appear in various forms, including both stable and unstable polymorphs. Indeed, PCC often represents a thermodynamically unstable calcium carbonate material. When referred to in the context of the present invention, PCC shall be understood to mean synthetic calcium carbonate products obtained notably by carbonation of a slurry of calcium hydroxide, commonly referred to in the art as a slurry of lime or milk of lime when derived from finely divided calcium oxide particles in water.
[0073] Preferred precipitated calcium carbonate is selected from aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
[0074] Additionally or alternatively, said GCC or PCC may be surface reacted to form a surface-modified calcium carbonate, which is a material comprising GCC and/or PCC and an insoluble, at least partially crystalline, non-carbonate calcium salt extending from the surface of at least part of the calcium carbonate. Such surface-modified products may, for example, be prepared according to WO 00/39222, WO 2004/083316, WO 2005/121257, WO 2009/074492, EP 2 264 108 A1, EP 2 264 109 A1.
[0075] The surface-modified calcium carbonate is obtained by reacting a natural calcium carbonate and/or precipitated calcium carbonate with an acid and with carbon dioxide prior to the preparation of the surface-treated calcium carbonate, wherein the carbon dioxide is formed in situ by the acid treatment and/or is supplied from an external source. The acid treatment can be carried out with an acid having a pKa at 25 °C of 6 or less. If the pKa at 25 °C is 0 or less, the acid is preferably selected from sulphuric acid, hydrochloric acid, or mixtures thereof. If the pKa at 25 °C is from 0 to 2.5, the acid is preferably selected from H2S03, M+HS04" (M+ is an alkali metal ion selected from the group comprising sodium and potassium), H3P04, oxalic acid or mixtures thereof. If the pKa at 25 °C is from 2.5 to 6, the acid is preferably selected from acetic acid, formic acid, propanoic acid and mixtures thereof. Furthermore, the subject-matters of EP 2 264 108 A1 and EP2 264 109 A1 relating to the acid treatment and the acid used for the acid treatment are hereby incorporated by reference in its entirety.
[0076] In an especially preferred embodiment, the calcium carbonate particles of the present surface-treated calcium carbonate have a weight median particle diameter d50 value of from 0.01 μίτι to 250 μίτι before surface treatment, preferably from 0.06 μίτι to 225 μίτι, more preferably from 1 μίτι to 200 μίτι, even more preferably from 1 μίτι to 150 μίτι and most preferably from 1 μίτι to 100 μίτι, measured according to the sedimentation process. Calcium carbonate particles having a d98of less than 100 microns, preferably of less than 85 microns may also be advantageous. Alternatively, calcium carbonate particles having a d98of less than 50 microns, preferably of less than 25 microns may be advantageous.
[0077] If the present surface-treated calcium carbonate comprises ground calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a weight median particle diameter d50 value of from 0.04 μίτι to 250 μίτι before surface treatment, more preferably from 0.06 μίτι to 225 μίτι, even more preferably from 1 μίτι to 200 μίτι, still more preferably from 1 μίτι to 150 μίτι and most preferably from 1 μίτι to 100 μίτι, measured according to the sedimentation process.
[0078] If the present surface-treated calcium carbonate comprises precipitated calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a weight median particle diameter d50 value of from 0.01 μίτι to 10 μίτι before surface treatment, more preferably from 0.02 μίτι to 5 μίτι, even more preferably from 0.02 μίτι to 2.5 μίτι and most preferably from 0.02 μίτι to 1 μίτι, measured according to the sedimentation process.
[0079] If the present surface-treated calcium carbonate comprises surface-modified calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a weight median particle diameter d50 value of from 0.5 μίτι to 150 μίτι before surface treatment, preferably from 0.5 μίτι to 100 μίτι, more preferably from 0.5 μίτι to 100 μίτι and most preferably from 1 μίτι to 50 μίτι, measured according to the sedimentation process.
[0080] As used herein and as generally defined in the art, the weight median particle diameter "dg8" value is defined as the size at which 98 % (the mean point) of the particle volume or mass is accounted for by particles having a diameter equal to the specified value. The weight median particle diameter was measured according to the sedimentation process. The sedimentation process is an analysis of sedimentation behaviour in a gravimetric field. The measurement is made with a Sedigraph™ 5100 of Micromeritics Instrument Corporation.
[0081] The calcium carbonate particles of the present surface-treated calcium carbonate preferably have a specific surface area of from 1 m2/g to 250 m2/g before surface treatment, more preferably 10 m2/g to 200 m2/g, even more preferably 20 m2/g to 150 m2/g and most preferably 30 m2/g to 100 m2/g, measured using nitrogen and the BET process. For example, the calcium carbonate particles of the surface-treated calcium carbonate have a specific surface area of from 40 m2/g to 50 m2/g before surface treatment, e.g. a specific surface area of 45 m2/g. Alternatively, the calcium carbonate particles of the present surface-treated calcium carbonate have a specific surface area of from 50 m2/g to 60 m2/g, e.g. a specific surface area of 56 m2/g.
[0082] If the present surface-treated calcium carbonate comprises ground calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a specific surface area of from 1 m2/g to 100 m2/g before surface treatment, more preferably 1 m2/g to 75 m2/g, even more preferably 1 m2/g to 50 m2/g and most preferably 1 m2/g to 20 m2/g, measured using nitrogen and the BET process.
[0083] If the present surface-treated calcium carbonate comprises precipitated calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a specific surface area of from 1 m2/g to 150 m2/g before surface treatment, more preferably 1 m2/g to 100 m2/g, even more preferably 1 m2/g to 70 m2/g and most preferably 1 m2/g to 50 m2/g, measured using nitrogen and the BET process.
[0084] If the present surface-treated calcium carbonate comprises surface-modified calcium carbonate, the calcium carbonate particles of the surface-treated calcium carbonate preferably have a specific surface area of from 1 m2/g to 250 m2/g before surface treatment, more preferably 1 m2/g to 200 m2/g, even more preferably 10 m2/g to 200 m2/g and most preferably 15 m2/g to 170 m2/g, measured using nitrogen and the BET process.
[0085] In one preferred embodiment, the calcium carbonate particles of the present surface-treated calcium carbonate have a specific surface area within the range of 1 m2/g to 250 m2/g and a weight median particle diameter d50 value within the range of 0.01 μίτι to 250 μίτι before surface treatment. Preferably, the specific surface area is within the range of 10 m2/g to 200 m2/g and the weight median particle diameter d50 value is within the range of 0.06 μίτι to 225 μίτι before surface treatment. More preferably, the specific surface area is within the range of 20 m2/g to 150 m2/g and the weight median particle diameter is within the range of 1 μίτι to 200 μίτι before surface treatment. Even more preferably, the specific surface area is within the range of 30 m2/g to 100 m2/g and the weight median particle diameter d50 value is within the range of 1 μίτι to 150 μίτι before surface treatment. Most preferably, the specific surface area is within the range of 30 m2/g to 100 m2/g and the weight median particle diameter d50 value is within the range of 1 μίτι to 100 μίτι before surface treatment. For example, the calcium carbonate particles of the present surface-treated calcium carbonate have a specific surface area within the range of 40 m2/g to 50 m2/g and a weight median particle diameter d50 value within the range of 1 μίτι to 50 μίτι. Alternatively, the calcium carbonate particles of the present surface-treated calcium carbonate have a specific surface area within the range of 50 m2/g to 60 m2/g and a weight median particle diameter d50 value within the range of 1 μίτι to 50 μίτι.
[0086] In accordance with the inventive process, at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer.
[0087] In this regard, the at least one cationic polymer being comprised in the coating of the surface-treated calcium carbonate may be selected from any cationic polymer having a positive charge density in the range of 1 mEq/g and 15 mEq/g. Preferably, the at least one cationic polymer is selected such that it has a positive charge density in the range of 2.5 mEq/g and 12.5 mEq/g and most preferably in the range of 5 mEq/g and 10 mEq/g.
[0088] For example, the at least one cationic polymer has a positive charge density in the range of 6 mEq/g and 8 mEq/g and most preferably in the range from 6 mEq/g and 7 mEq/g. Alternatively, the at least one cationic polymer has a positive charge density in the range of 7 mEq/g and 8 mEq/g.
[0089] Additionally or alternatively, the at least one cationic polymer being comprised in the coating of the surface-treated calcium carbonate is selected such that at least 60 % of the monomer units carry a cationic charge. Preferably, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer in which at least 70 % of the monomer units have a cationic charge, more preferably at least 80 % and even more preferably at least 90 %. In one preferred embodiment of the present invention, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer in which equal to 100 %, preferably 100 %, of the monomer units have a cationic charge.
[0090] In one preferred embodiment, the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer having a weight average molecular weight Mw of below 1,000,000 g/mole, more preferably from 50,000 to 750,000 g/mole, even more preferably from 50,000 to 650,000 g/mole and most preferably from 100,000 to 300,000 g/mole.
[0091] In the process of the present invention, the surface-treated calcium carbonate is covered by a coating comprising a homopolymer and/or a copolymer of the at least one cationic polymer.
[0092] In one preferred embodiment, the coating of the at least one surface-treated calcium carbonate comprises a homopolymer of the at least one cationic polymer. That is to say, the cationic polymer consists substantially, i.e. of equal or below than 99.5 wt.-%, of the respective monomer units.
[0093] In one preferred embodiment, only monomer units selected from the group consisting of diallyldialkyl ammonium salts, tertiary amines, quaternized amines, quaternized imines, are electable in the homopolymer.
[0094] In one preferred embodiment of the present invention, the coating of the at least one surface-treated calcium carbonate comprises a homopolymer based on diallyldialkyl ammonium salt monomers. In one preferred embodiment, the diallyldialkyl ammonium salt monomers are diallyldimethyl ammonium chloride.
[0095] In case the cationic polymer is a copolymer, it is appreciated that the copolymer comprises monomers copol-ymerizable with suitable comonomers. Preferably, the cationic polymer being a copolymer according to this invention comprises, preferably consists of, monomer units selected from diallyldialkyl ammonium salts and comonomer units selected from the group consisting of acrylamide, methacrylamide, Ν,Ν-dimethyl acrylamide, acrylic acid, methacrylic acid, vinylsulfonic acid, vinyl pyrrolidone, hydroxyl ethyl acrylate, styrene, methyl methacrylate, vinyl acetate and mixtures thereof.
[0096] For example, the coating of the surface-treated calcium carbonate may comprise a cationic polymer as described as comb polymer in US 2009/0270543 A1.
[0097] In one preferred embodiment, the cationic polymer is a copolymer prepared from 92 wt.-% methoxy polyethylene glycol methacrylate of molecular weight 2,000 g/mole and 8 wt.-% acrylic acid and at least partially neutralised by soda. In a further preferred embodiment, the cationic polymer is a copolymer prepared from 92 wt.-% methoxy polyethylene glycol methacrylate of molecular weight 2,000 g/mole and 8 wt.-% acrylic acid and totally neutralised by soda.
[0098] If the monomer and/or comonomer units of the homopolymer or copolymer are diallyldialkyl ammonium salts, they are preferably selected from the group consisting of diallyldimethyl ammonium bromide, diallyldimethyl ammonium chloride, diallyldimethyl ammonium phosphate, diallyldiethyl ammonium sulfate, diallyldiethyl ammonium bromide, dial-lyldiethyl ammonium chloride, diallyldiethyl ammonium phosphate, diallyldiethyl ammonium sulphate, diallyldipropyl ammonium bromide, diallyldipropyl ammonium chloride, diallyldipropyl ammonium phosphate and diallyldipropyl ammonium sulphate. In one preferred embodiment, the diallyldialkyl ammonium salt monomers are diallyldimethyl ammonium chloride monomers.
[0099] In an especially preferred embodiment, the cationic polymer is a homopolymer based on diallyldimethyl ammonium chloride (PolyDADMAC).
[0100] If the monomer and/or comonomer units of the homopolymer or copolymer are quaternized amines, they are preferably epichlorhydrin reaction products such as polyamine epichlorhydrin.
[0101] If the monomer and/or comonomer units of the homopolymer or copolymer are quaternized imines, they are preferably polyethyleneimine.
[0102] In one preferred embodiment, the cationic polymer of this invention being a copolymer comprising monomer units selected from diallyldialkyl ammonium salts, and acrylamide or acrylic acid as comonomer units.
[0103] For example, the coating of the at least one surface-treated calcium carbonate comprises a copolymer of the at least one cationic polymer, wherein the monomer and comonomer units are derivable from diallyldialkyl ammonium salts and acrylamide only. In one preferred embodiment, the cationic polymer being a copolymer of this invention comprises monomer and comonomer units derivable from diallyldimethyl ammonium chloride and acrylamide only. Alternatively, the coating of the at least one surface-treated calcium carbonate comprises a copolymer of the at least one cationic polymer, wherein the monomer and comonomer units are derivable from methacrylic acid and acrylic acid only.
[0104] Additionally or alternatively, the coating of the at least one surface-treated calcium carbonate comprises a copolymer of the at least one cationic polymer, wherein the monomer and comonomer units are derivable from acrylic acid and acrylamide only.
[0105] Additionally, it is appreciated that the copolymer has preferably a comonomer content of more than 2.0 wt.-%, more preferably more than 5 wt.-%, yet more preferably more than 7.5 wt.-%. For example, the copolymer has preferably a comonomer content in the range between 2 wt.-% and 80 wt.-%, more preferably in the range between 5 wt.-% and 60 wt.-% and most preferably in the range between 7.5 wt.-% and 40 wt.-%. The weight percentage is based on the total weight of the copolymer.
[0106] In one preferred embodiment, the coating of the at least one surface-treated calcium carbonate comprises a copolymer, wherein the molar ratio of monomer units and comonomer units is from 5:1 to 1:5, more preferably from 4:1 to 1:4, even more preferably from 3:1 to 1:3 and most preferably from 3:1 to 1:1.
[0107] In one preferred embodiment, the cationic polymer comprises a mixture of at least two cationic polymers. Preferably, if the cationic polymer comprises a mixture of at least two cationic polymers, one cationic polymer is a homopolymer based on diallyldimethyl ammonium chloride.
[0108] In a further preferred embodiment, the cationic polymer comprises a mixture of two cationic polymers, wherein one cationic polymer is a homopolymer based on diallyldimethyl ammonium chloride and the other one is selected from the group consisting of a copolymer based on diallyldimethyl ammonium chloride and acrylamide.
[0109] If the cationic polymer comprises a mixture of two cationic polymers, the molar ratio of the homopolymer based on diallyldimethyl ammonium chloride and the second cationic polymer is from 99:1 to 1:99, more preferably from 50:1 to 1:50, even more preferably from 25:1 to 1:25 and most preferably from 10:1 to 1:10. In one especially preferred embodiment of the present invention, the molar ratio of the homopolymer based on diallyldimethyl ammonium chloride and the second cationic polymer is from 90:1 to 1:1, more preferably from 90:1 to 10:1 and most preferably from 90:1 to 50:1.
[0110] The at least one cationic polymer is preferably present in the coating covering the calcium carbonate in a quantity such that the total weight of said at least one cationic polymer on the surface of the surface-treated calcium carbonate product is between 0.01% w/w and 80 % w/w of the calcium carbonate.
[0111] In one preferred embodiment, the at least one cationic polymer is present in the coating covering the calcium carbonate in a quantity such that the total weight of said at least one cationic polymer on the surface of the surface-treated calcium carbonate product is less than 80 % w/w, more preferably less than 60 % w/w and most preferably less than 50 % w/w of the calcium carbonate.
[0112] In another preferred embodiment, the at least one cationic polymer is present in the coating covering at least 1 % of the accessible surface area of the calcium carbonate in an amount of aboutO.1 wt.-% to 30 wt.-%, more preferably of about 0.1 wt.-% to 20 wt.-%, even more preferably of about 0.2 wt.-% to 15 wt.-% and most preferably of about 0.2 wt.-% to 10 wt.-%, based on the dry weight of the calcium carbonate.
[0113] Alternatively, at least 10 % of the accessible surface area of the calcium carbonate particles is covered by a coating comprising the at least one cationic polymer. In a preferred embodiment, at least 20 % of the accessible surface area of the calcium carbonate particles is covered by a coating comprising the at least one cationic polymer, preferably at least 30 % of the accessible surface area, more preferably at least 40 % of the accessible surface area and most preferably at least 50 % of the accessible surface area. In another preferred embodiment, at least 75 % of the accessible surface area of the calcium carbonate particles is covered by a coating comprising the at least one cationic polymer. For example, at least 90 % of the accessible surface area of the calcium carbonate particles is covered by a coating comprising the at least one cationic polymer.
[0114] In one preferred embodiment, at least 75 % of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is covered by a coating comprising a homopolymer based on diallyldimethyl ammonium chloride. In another preferred embodiment, at least 75 % of the aliphatic carboxylic acid accessible surface area of the calcium carbonate particles is covered by a coating comprising a homopolymer based on acrylic acid.
[0115] In one preferred embodiment, the at least one cationic polymer has a solubility in water of above 50 g/100 ml of water, preferably of above 75 g/100 ml of water, even more preferably of above 100 g/100 ml of water and most preferably of above 150 g/100 ml of water. In one especially preferred embodiment, the at least one cationic polymer is readily soluble in water.
[0116] Preferably, the surface-treated calcium carbonate used in the present process is prepared by mixing the ground calcium carbonate and/or precipitated calcium carbonate and/or surface-modified calcium carbonate, preferably in form of slurry, and the cationic polymer, preferably in form of a suspension, before being brought into contact with the water to be treated. Mixing can be accomplished by any conventional means known to the skilled person.
[0117] The surface-treated calcium carbonate is preferably in theform ofa particulate material, and may have a particle size distribution as conventionally employed for the material(s) involved in the treatment of polluted water. In general, the weight median particle diameter d50 value of the surface-treated calcium carbonate is in the range between 0.01 μίτι and 250 μίτι, preferably between 0.06 μίτι and 225 μίτι, more preferably between 1 μίτι and 200 μίτι, even more preferably between 1 μίτι and 150 μίτι, and most preferably between 1 μίτι and 100 μίτι, measured according to the sedimentation process. A surface-treated calcium carbonate having a dg8 of less than 100 microns, preferably of less than 85 microns may also be advantageous. Alternatively, surface-treated calcium carbonate having a dg8 of less than 50 microns, preferably of less than 25 microns may be advantageous.
[0118] If the surface-treated calcium carbonate comprises ground calcium carbonate, the surface-treated calcium carbonate preferably has a weight median particle diameter d50 value of from 0.04 μίτι to 250 μίτι, more preferably from 0.06 μίτι to 225 μίτι, even more preferably from 1 μίτι to 200 μίτι, still more preferably from 1 μίτι to 150 μίτι and most preferably from 1 μίτι to 100 μίτι, measured according to the sedimentation process.
[0119] If the surface-treated calcium carbonate comprises precipitated calcium carbonate, the surface-treated calcium carbonate preferably has a weight median particle diameter d50 value of from 0.01 μίτι to 10 μίτι, more preferably from 0.02 μίτι to 5 μίτι, even more preferably from 0.02 μίτι to 2.5 μίτι and most preferably from 0.02 μίτι to 1 μίτι, measured according to the sedimentation process.
[0120] If the surface-treated calcium carbonate comprises surface-modified calcium carbonate, the surface-treated calcium carbonate preferably has a weight median particle diameter d50 value of from 0.5 μίτι to 150 μίτι, preferably from 0.5 μίτι to 100 μίτι, more preferably from 0.5 μίτι to 100 μίτι and most preferably from 1 μίτι to 50 μίτι, measured according to the sedimentation process. In a preferred embodiment, the surface-treated calcium carbonate may be in the form of agglomerated particles, having a weight median particle diameter d50 value of from 0.5 μίτι to 250 μίτι and preferably from 0.5 μίτι to 150 μίτι measured according to the sedimentation process.
[0121] The surface-treated calcium carbonate preferably has a specific surface area of from 1 m2/g to 250 m2/g, preferably 20 m2/g to 200 m2/g, more preferably 30 m2/g to 150 m2/g and most preferably 30 m2/g to 100 m2/g, measured using nitrogen and the BET process. For example, the surface-treated calcium carbonate has a specific surface area of from 40 m2/g to 50 m2/g, e.g. a specific surface area of 45 m2/g. Alternatively, the surface-treated calcium carbonate has a specific surface area of from 50 m2/g to 60 m2/g, e.g. a specific surface area of 56 m2/g.
[0122] If the surface-treated calcium carbonate comprises ground calcium carbonate, the surface-treated calcium carbonate preferably has a specific surface area of from 1 m2/g to 100 m2/g, more preferably 1 m2/g to 75 m2/g, even more preferably 1 m2/g to 50 m2/g and most preferably 1 m2/g to 20 m2/g, measured using nitrogen and the BET process.
[0123] If the surface-treated calcium carbonate comprises precipitated calcium carbonate, the surface-treated calcium carbonate preferably has a specific surface area of from 1 m2/g to 150 m2/g, more preferably 1 m2/g to 100 m2/g, even more preferably 1 m2/g to 70 m2/g and most preferably 1 m2/g to 50 m2/g, measured using nitrogen and the BET process.
[0124] If the surface-treated calcium carbonate comprises surface-modified calcium carbonate, the surface-treated calcium carbonate preferably has a specific surface area of from 1 m2/g to 250 m2/g before surface treatment, more preferably 1 m2/g to 200 m2/g, even more preferably 10 m2/g to 200 m2/g and most preferably 15 m2/g to 170 m2/g, measured using nitrogen and the BET process.
[0125] In one preferred embodiment, the at least one surface-treated calcium carbonate has a specific surface area within the range of 1 m2/g to 250 m2/g and a weight median particle diameter d50 value within the range of 0.01 μίτι to 250 μίτι. Preferably, the specific surface area is within the range of 20 m2/g to 200 m2/g and the weight median particle diameter d50 value is within the range of 0.06 μίτι to 225 μίτι. More preferably, the specific surface area is within the range of 30 m2/g to 150 m2/g and the weight median particle diameter is within the range of 1 μηι to 200 μηι. Even more preferably, the specific surface area is within the range of 30 m2/g to 100 m2/g and the weight median particle diameter d50 value is within the range of 1 μίτι to 150 μίτι. Most preferably, the specific surface area is within the range of 30 m2/g to 100 m2/g and the weight median particle diameter d50 value is within the range of 1 μίτι to 100 μίτι. For example, the at least one surface-treated calcium carbonate has a specific surface area within the range of 40 m2/g to 50 m2/g and a weight median particle diameter d50 value within the range of 1 μίτι to 50 μίτι. Alternatively, the at least one surface-treated calcium carbonate has a specific surface area within the range of 50 m2/g to 60 m2/g and a weight median particle diameter d50 value within the range of 1 μΐη to 50 μηι [0126] The surface-treated calcium carbonate to be used in the process can be present in any appropriate form, e.g. in the form of granules and/or a powder or in the form of a cake. Preferably, the surface-treated calcium carbonate to be used in the inventive process is in powderform and/or in theform of granules. In a preferred embodiment, the surface- treated calcium carbonate to be used in the inventive process is in powderform. Alternatively, the surface-treated calcium carbonate to be used in the inventive process can be present as an aqueous suspension, e.g. in the form of a slurry or a paste which can be metered with a conveying screw.
[0127] Said slurry may comprise at least one further cationic polymer, wherein said cationic polymer can be the same cationic polymer used for coating or a different cationic polymer, e.g. a further cationic polymer as described herein. After coating the slurry may be used directly without further purification, or at least one furher cationic polymer may be added to the slurry.
[0128] A "slurry" or "suspension" in the meaning of the present invention comprises undissolved solids, i.e. surface-treated calcium carbonate and water and optionally further additives. Suspensions usually contain large amounts of solids and are more viscous and generally of higher density than the liquid from which they are formed. It is accepted in the art that the general term "dispersion" inter alia covers "suspensions" or "slurries" as a specific type of dispersion.
[0129] In one preferred embodiment, the surface-treated calcium carbonate to be used in the process is suspended in water such that the slurry has a content of surface-treated calcium carbonate within the range of 1 wt.-% to 80 wt.-%, more preferably 3 wt.-% to 60 wt.-%, and even more preferably 5 wt.-% to 50 wt.-%, based on the weight of the slurry.
Step c) contacting the water and/or sludge and/or sediment with the at least one surface-treated calcium carbonate [0130] According to step c) of the process, the water to be purified and/or sludge and/or sediment to be dewatered provided in step a) is contacted with the at least one surface-treated calcium carbonate of step b) for obtaining a composite material of surface-treated calcium carbonate and impurities from different sources. In general, the water to be purified and/or sludge and/or sediment to be dewatered and the surface-treated calcium carbonate can be brought into contact by any conventional means known to the skilled person.
[0131] For example, the step of contacting the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer, preferably takes place in that the surface of the polluted water and/or sludge and/or sediment is at least partially covered with the at least one surface-treated calcium carbonate. Additionally or alternatively, the step of contacting the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate preferably takes place in that the polluted water and/or sludge and/or sediment of step a) is mixed with the surface-treated calcium carbonate of step b). The skilled man will adapt the mixing conditions (such as the configuration of mixing speed) according to his needs and available equipment.
[0132] Preferably, the surface-treated calcium carbonate is suspended in the water and/or sludge and/or sediment to be treated, e.g. by agitation means.
[0133] The treatment time for carrying out the contacting of the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate is carried out for a period in the range of several seconds to several minutes, e.g. 20 s or more, preferably 30 s or more, more preferably 60 s or more and most preferably for a period of 120 s or more. In general, the length of contacting the water and/or sludge and/or sediment to be treated with the at least one surface-treated calcium carbonate is determined by the degree of water and/or sludge and/or sediment pollution and the specific water and/or sludge and/or sediment to be treated.
[0134] It is to be understood that the amount of surface-treated calcium carbonate according to the present process is selected such that it is sufficient in the water and/or sludge and/or sediment to be treated, i.e. high enough for providing efficient binding activity for at least one type of inorganic impurities present in the polluted water and/or sludge and/or sediment but at the same time is so low that no significant amount of unbound surface-treated calcium carbonate would be observed in the water and/or sludge and/or sediment to treated.
[0135] The amount of surface-treated calcium carbonate depends on the type of water and/or sludge and/or sediment to be treated as well as on the type and amount of impurities. Preferably, an amount of 10 ppm to 1 wt.-%, more preferably 100 ppm to 0.2 wt.-% surface-treated calcium carbonate, based on the total weight of the water and/or sludge and/or sediment to be treated, is added.
[0136] The surface-treated calcium carbonate can be added as an aqueous suspension, e.g. the suspension described above. Alternatively, it can be added to the water to be purified and/or sludge and/or sediment to be dewatered in any appropriate solid form, e.g. in the form of granules or a powder or in form of a cake.
[0137] Within the context of the present invention, it is also possible to provide an immobile phase, e.g. in the form of a cake or layer, comprising the surface-treated calcium carbonate, the water and/or sludge and/or sediment to be treated running through said immobile phase.
[0138] In a preferred embodiment, the water and/or sludge and/orsedimentto be purified is passed through a permeable filter comprising the surface-treated calcium carbonate and being capable of retaining, via size exclusion, the inorganic impurities on the filter surface as the liquid is passed through by gravity and/or under vacuum and/or under pressure. This process is called "surface filtration".
[0139] In another preferred technique known as depth filtration, a filtering aid comprising a number of tortuous passages of varying diameter and configuration retains impurities by molecular and/or electrical forces adsorbing the impurities onto the surface-treated calcium carbonate which is present within said passages, and/or by size exclusion, retaining the impurity particles if they are too large to pass through the entire filter layer thickness.
[0140] The techniques of depth filtration and surface filtration may additionally be combined by locating the depth filtration layer on the surface filter; this configuration presents the advantage that those particles that might otherwise block the surface filter pores are retained in the depth filtration layer.
[0141] In one preferred embodiment of the present invention, the process further comprises step d) of contacting the water to be purified and/or sludge and/or sediment to be dewatered with at least one polymeric flocculation aid.
[0142] In a preferred embodiment of the present invention, the polymeric flocculation aid and the surface-treated calcium carbonate are added simultaneously to the water and/or sludge and/or sediment to be treated. In another preferred embodiment of the present invention, the polymeric flocculation aid and the surface-treated calcium carbonate are added separately to the water and/or sludge and/or sediment to be treated. In this case, the water and/or sludge and/or sediment to be treated is first contacted with the surface-treated calcium carbonate and then with the polymeric flocculation aid.
[0143] For example, the polymeric flocculation aid is added to the water and/or sludge and/or sediment to be treated when adsorption of impurities on the surface-treated calcium carbonate has reached its maximum, i.e. there is no further decrease of inorganic impurities within the water. However, it is also possible to add the polymeric flocculation aid at an earlier stage, e.g. when at least 50%, at least 70% or at least 90% of maximum adsorption of impurities on the surface-treated calcium carbonate has been reached.
[0144] The step of contacting the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate and the polymeric flocculation aid preferably takes place in that the surface of the water and/or sludge and/or sediment is at least partially covered, either simultaneously or separately, with the at least one surface-treated calcium carbonate and the polymeric flocculation aid. Additionally or alternatively, the step of contacting the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate and the polymeric flocculation aid preferably takes place in that the water and/or sludge and/or sediment is, either simultaneously or separately, mixed with the surface-treated calcium carbonate and the polymeric flocculation aid. The skilled man will adapt the mixing conditions (such as the configuration of mixing speed) according to his needs and available equipment.
[0145] The treatment time for carrying out the contacting of the water to be purified and/or sludge and/or sediment to be dewatered with the at least one surface-treated calcium carbonate and the polymeric flocculation aid is carried out for a period in the range of several seconds to several minutes, e.g. 30 s or more, preferably 60 s or more, more preferably 90 s or more and most preferably for a period of 180 s or more. In general, the length of contacting the water and/or sludge and/or sediment to be treated with the at least one surface-treated calcium carbonate and the polymeric flocculation aid is determined by the degree of water pollution and the specific water and/or sludge and/or sediment to be treated.
[0146] In a preferred embodiment of the present invention, process step c) and step d) are repeated one or more times. In a preferred embodiment of the present invention, process step c) or step d) is repeated one or more times. If step c) and step d) are repeated one or more times, step c) and step d) may be repeated independently, i.e. step c) may be repeated several times, while step d) is repeated more or less times than step c) and vice versa. For example, step c) may be repeated twice, while step d) is repeated once or more than twice.
[0147] Any polymeric flocculation aid known in the art can be used in the process of the present invention. Examples of preferred polymeric flocculation aids include polyacrylamides or polyelectrolytes based on poly aery lates, poly(dial-lyldimethylammonium chloride), polyethyleneimines, polyamines or mixtures of these, and natural polymers such as starch, or natural modified polymers like modified carbohydrates.
[0148] In a preferred embodiment, the polymeric flocculation aid is no polyacrylamide.
[0149] Preferably, the polymeric flocculation aid has a weight average molecular weight of at least 100,000 g/mole. In a preferred embodiment, the polymeric flocculation aid has a weight average molecular weight Mw in the range from 100,000 to 10,000,000 g/mole, preferably in the range from 300,000 to 5,000,000 g/mole, more preferably in the range from 300,000 to 1,000,000 g/mole and most preferably in the range from 300,000 to 800,000 g/mole.
[0150] The polymeric flocculation aid can be ionic or non-ionic. Preferably, the polymeric flocculation aid is ionic, i.e. an anionic polymeric flocculation aid ora cationic polymeric flocculation aid.
[0151] In the context of the present invention, the term "cationic" refers to any polymer having a positive overall charge. Thus, the presence of some anionic monomer units is not excluded as long as there are still sufficient cationic monomer units providing a positive overall charge and enabling its use as a flocculation aid. Furthermore, the term "cationic polymeric flocculation aid" also comprises those polymers having monomer units with functional groups which become cationic upon addition to the water to be treated, e.g. amine groups becoming ammonium groups in acidic water.
[0152] The term "anionic" refers to any polymer having a negative overall charge. Thus, the presence of some cationic monomer units is not excluded as long as there are still sufficient anionic monomer units providing a negative overall charge and enabling its use as a flocculation aid. Furthermore, the term "anionic polymeric flocculation aid" also comprises those polymers having monomer units with functional groups which become anionic upon addition to the water to be treated, e.g. acid groups such as sulfonic acid groups.
[0153] A preferred polymeric flocculation aid of the present invention is polyacrylamide. By appropriate modifications which are known to the skilled person, the polyacrylamide can be used as a cationic polymeric flocculation aid as well as an anionic polymeric flocculation aid.
[0154] Preferably, the polyacrylamide contains at least 50 mol-%, more preferably at least 60 mol-%, even more preferably at least 75 mol-% monomer units derived from acrylamide.
[0155] An anionic polyacrylamide, i.e. a polyacrylamide having a negative overall charge, can be obtained by introducing appropriate comonomer units, e.g. derived from (meth)acrylic acid.
[0156] A cationic polyacrylamide, i.e. a polyacrylamide having a positive overall charge, can be obtained by introducing appropriate comonomer units, e.g. derived from aminoalkyl(meth)acrylatessuch as dimethylaminomethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, dimethylaminopro-pyl(meth)acrylate, diethylaminomethyl(meth)acrylate, diethylami-noethyl(meth)acrylate or diethylaminopropyl(meth)acrylate which can be quaternized by alkyl halides.
[0157] In another preferred embodiment, polyacrylate is used as a preferred polymeric flocculation aid in the process. Preferably, the polyacrylate is used as a cationic polymeric flocculation aid. More specifically, the polyacrylate used as a cationic polymeric flocculation aid is free of acrylamide.
[0158] Preferably, the polyacrylate contains at least 50 mol-%, more preferably at least 60 mol-%, even more preferably at least 75 mol-% monomer units derived from aminoalkyl(meth)acrylates such as dimethylaminomethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, dimethylaminopro-pyl(meth)acrylate, diethylaminomethyl(meth)acrylate, diethylami-noethyl(meth)acrylate or diethylaminopropyl(meth)acrylate which can be quaternized by alkyl halides. Alternatively, the polymeric flocculation aid may be a polymer as described as comb polymer in US 2009/0270543 A1.
[0159] In one preferred embodiment, the polymeric flocculation aid is a copolymer prepared from 92 wt.-% methoxy polyethylene glycol methacrylate of molecular weight 2,000 g/mole and 8 wt.-% acrylic acid and at least partially neutralised by soda. In a further preferred embodiment, the polymeric flocculation aid is a copolymer prepared from 92 wt.-% methoxy polyethylene glycol methacrylate of molecular weight 2,000 g/mole and 8 wt.-% acrylic acid and totally neutralised by soda.
[0160] Optionally, further additives can be added to the water and/or sludge and/or sediment to be treated. These might include agents for pH adjustment and conventional flocculants such as polyaluminium chloride, iron chloride or aluminium sulphate. However, in a preferred embodiment, the water purification process and/or dewatering process of sludge and/or sediment of the present invention does not use any additional conventional inorganic flocculation aids such as polyaluminium chloride, iron chloride or aluminium sulphate.
[0161] After the contacting/flocculation has been completed, the flocculated composite material can be removed from the treated water by conventional separation means known to the skilled person such as filtration, sedimentation and/or centrifugation.
[0162] In an alternative approach, the water to be purified and/or sludge and/or sediment to be dewatered is preferably passed through a permeable filter comprising the surface-treated calcium carbonate and being capable of retaining, via size exclusion, the impurities on the filter surface as the filtrate is passed through by gravity and/or under vacuum and/or under pressure. This process is called "surface filtration".
[0163] In accordance with the present invention, the process for the purification of water and/or dewatering of sludge and/or sediment is suitable for effectively reducing the amount of polymeric flocculation aid contained in a purified water sample and/or dewatered sludge and/or sediment sample.
[0164] In a preferred embodiment, the water and/or sludge and/or sediment obtained by the process of the present invention contains an amount of polymeric flocculation aid of at least 10 wt.-%, preferably at least 20 wt.-%, more preferably at least 30 wt.-%, even more preferably at least 40 wt.-%, still more preferably at least 50 wt.-% and most preferably at least 60 wt.-% below the amount of free flocculation aid contained in corresponding water and/or sludge and/or sediment being treated the same way but in the absence of the at least one surface-treated calcium carbonate. For example, the water and/or sludge and/or sediment obtained by the process contains an amount of polymeric flocculation aid of at least 70 wt.-%, preferably at least 80 wt.-% and most preferably at least 90 wt.-% below the amount of free flocculation aid contained in corresponding water and/or sludge and/or sediment being treated the same way but in the absence of the at least one surface-treated calcium carbonate.
[0165] The use of the process for the purification of water and/or dewatering of sludges and/or sediments provides a number of improved properties. First of all, the inventive use provides excellent binding activity for impurities when the at least one surface-treated calcium carbonate is at least partially applied onto the surface of the water and/or sludge and/or sediment to be treated or mixed with the water and/or sludge and/or sediment to be treated. Furthermore, the use of the process results in a composite material of surface-treated calcium carbonate and impurities which can be easily removed from the medium to be treated. Furthermore, the binding of impurities by the inventive process results in a good cleansing quality of the water and/or sludge and/or sediment to be treated as well as of the obtained filter cake. A further advantage of the process resides in the fact that the used surface-treated calcium carbonate lowers the amount of polymeric flocculation aid in the treated water and/or sludge and/or sediment and thus decreases the disturbance of the ecological balance. Another advantage of the process is that the quality of the obtained filter cake is increased so that the subsequent disposal is less energy-consuming.
[0166] Depending on the specific requirements and/or the respective physical and/or chemical properties of the water and/or sludge and/or sediment to be treated, the surface-treated calcium carbonate and the optional polymeric flocculation aid to be used according to the process can be applied both separately or a finished mixture may be used. In the form of a separately metered addition of the individual components of the surface-treated calcium carbonate and the optional polymeric flocculation aid, the concentration ratio may be individually adjusted depending on the present water and/or sludge and/or sediment to be treated. The water and/or sludge and/or sediment may be treated with the surface-treated calcium carbonate being formulated, for example, as a customary formulation, such as, for example, a slurry, a powder or granules.
[0167] Applications are possible for the purification of water and dewatering of sludges and/or sediments originated in different industries such as industrial waste water, drinking water, urban waste water, sludge such as harbour sludge, river sludge, coastal sludge or digested sludge, waste water or process waterfrom breweries or other beverage industries, waste water or process water in the paper industry, colour-, paints-, or coatings industry, agricultural waste water, slaughterhouse waste water, leather industry waste water and leather tanning industry.
[0168] In a preferred embodiment, the surface-treated calcium carbonate can also be advantageously used for neutralizing or buffering the water and/or sludge and/or sediment to be treated, such as industrial waste water, drinking water, urban waste water, sludge such as harbour sludge, river sludge, coastal sludge or digested sludge, waste water or process waterfrom breweries or other beverage industries, waste water or process water in the paper industry, colour-, paints-, or coatings industry, agricultural waste water, slaughterhouse waste water, leather industry waste water and leather tanning industry.
[0169] In view of the very good results of the process in the purification of water and/or dewatering of sludges and/or sediments as defined above, an aspect of the present invention is the use of the surface-treated calcium carbonate in the purification of water and/or dewatering of sludges and/or sediments. According to another aspect of the present invention, the use of the surface-treated calcium carbonate for reducing the amount of polymeric flocculation aids in water and/or sludges and/or sediments is provided.
[0170] According to a further aspect of the present invention, a composite material comprising the surface-treated calcium carbonate and impurities is provided.
[0171] Preferably, the composite material further comprises a polymeric flocculation aid as defined above. When the surface-treated calcium carbonate is used in combination with a polymeric flocculation aid as defined above, it has surprisingly been found that a flocculated composite material of improved compactness is obtained while the concentration of polymeric flocculation aid in the filtrate is considerably reduced.
[0172] If the flocculated composite material is separated from the water and/or sludge and/or sediment by filtration, sedimentation and/or centrifugation, the composite material can be present in the form of a filter cake.
[0173] With regard to the definition of the surface-treated calcium carbonate and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the process of the present invention.
[0174] The following examples may additionally illustrate the invention, but are not meant to restrict the invention to the exemplified embodiments.
EXAMPLES
Measurement processes [0175] Thefollowing measurement processes were used to evaluate the parameters given in the examples and claims. BET specific surface area of a material [0176] The BET specific surface area was measured via the BET process according to ISO 9277 using nitrogen, following conditioning of the sample by heating at 250°C for a period of 30 minutes. Prior to such measurements, the sample was filtered, rinsed and dried at 110°C in an oven for at least 12 hours.
Particle size distribution (mass % particles with a diameter <X) and weight median diameter (d50) of a particulate material [0177] Weight median grain diameter and grain diameter mass distribution of a particulate material were determined via the sedimentation process, i.e. an analysis of sedimentation behaviour in a gravitational field. The measurement was made with a Sedigraph™ 5100.
[0178] The weight median grain diameter of the surface reacted calcium carbonate was determined by using a Malvern Mastersizer 2000 Laser Diffraction System.
[0179] The processes and instruments are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurements were carried out in an aqueous solution of 0.1 wt.-% Na4P207. The samples were dispersed using a high speed stirrer and ultrasound.
Accessible surface area [0180] The accessible surface area of the calcium carbonate may be determined by the process described in the publication of Papirer, Schultz and Turchi (Eur. Polym. J., Vol. 20, No. 12, pp. 1155-1158, 1984).
Haze [0181] The haze of the water samples is measured by using a standard photometer in accordance with standard procedures. pH measurement [0182] The pH of the water samples is measured by using a standard pH-meter at approximately 25°C.
Alkalinity [0183] The alkalinity of the water samples is measured by using standard titration procedures.
Oxydizability [0184] The oxydizability of the water samples is measured by using the well known CSB method using potassium dichromate.
Example 1 [0185] The following illustrative Example involves the use of a surface-treated calcium carbonate in combination with a polymeric flocculation aid for the purification of two different sludge samples. Said surface-treated calcium carbonate comprises a modified calcium carbonate and has a weight medium particle diameter d50 value of 1.6 μίτι (measured according to the sedimentation process) and a specific surface area of 45 m2/g (measured using nitrogen and the BET process), before surface treatment. The surface-treated natural calcium carbonate is covered by a coating comprising polyacrylate having a cationic charge density of 7 mEq/g. The polyacrylate is present in the coating in an amount of 0.95 wt.-%, based on the dry weight of the calcium carbonate. As the polymeric flocculation aid, the commercially available flocculation aid FLOPAM™ FB 608 (commercially available from SNF Floerger, France) was used.
[0186] The purification process was performed on a mixed sludge (a blend of a primary and biological sludge) sampled from STEP Collombey-Muraz and a digested sludge sampled from STEP AIEE Penthaz. 200 ml of the respective sludge sample was added to a slurry of surface-treated calcium carbonate having a content of surface-treated calcium carbonate of 44.2 wt.-%, based on the total weight of the slurry. After manual agitation, the flocculation was completed by adding the polymeric flocculation aid. The polymeric flocculation aid was used in the form of a suspension having a content of flocculation aid of 0.5 wt.-%, based on the total weight of the suspension. The content of flocculation aid in the sample was monitored for the respective sludge samples. Tables 1 and 2 summary the details of the utilized amounts of surface-treated calcium carbonate and the measured reduction of polymeric flocculation aid.
Table 1 : results for the mixed sludge
(continued)
Table 2: results for the digested sludge
[0187] During the purification process of the mixed sludge as well as for the digested sludge samples treated with a combination of the surface-treated calcium carbonate and a polymeric flocculation aid, a concentration reduction in the range of about 42 to 47 % was obtained for the polymeric flocculation aid. It can thus be concluded that during the purification process a reduced amount of polymeric flocculation aid is needed.
Example 2 [0188] The following illustrative Example involves the use of a surface-treated calcium carbonate in combination with a polymeric flocculation aid for the purification of two different sludge samples. Said surface-treated calcium carbonate comprises a modified calcium carbonate and has a weight medium particle diameter d50 value of 2.0 μίτι (measured according to the sedimentation process) and a specific surface area of 56 m2/g (measured using nitrogen and the BET process), before surface treatment. The surface-treated natural calcium carbonate is covered by a coating comprising poly(diallyldimethylammonium chloride) having a cationic charge density of 6.2 mEq/g. The poly(diallyldimethylammo-nium chloride) is present in the coating in an amount of 1.5 wt.-%, based on the dry weight of the calcium carbonate. As the polymeric flocculation aid, the commercially available flocculation aid FLOP AM™ FB 608 (commercially available from SNF Floerger, France) was used.
[0189] The purification process was performed on a mixed sludge (a blend of a primary and biological sludge) sampled from STEP Collombey-Muraz and a digested sludge sampled from STEP AIEE Penthaz. 200 ml of the respective sludge sample was added to a slurry of surface-treated calcium carbonate having a content of surface-treated calcium carbonate of 31.0 wt.-%, based on the total weight of the slurry. After manual agitation, the flocculation was completed by adding the polymeric flocculation aid. The polymeric flocculation aid was used in the form of a suspension having a content of flocculation aid of 0.5 wt.-%, based on the total weight of the suspension. The content of polymeric flocculation aid in the sample was monitored for the respective sludge samples. Tables 3 and 4 summary the details of the utilized amounts of surface-treated calcium carbonate and the measured reduction of polymeric flocculation aid.
Table 3: results for the mixed sludge
(continued)
Table 4: results for the digested sludge
[0190] During the purification process of the mixed sludge as well as for the digested sludge samples treated with a combination of the surface-treated calcium carbonate and a polymeric flocculation aid, a concentration reduction in the range of about 61 to 67 % for the polymeric flocculation aid was observed. It can thus be concluded that during the purification process a reduced amount of polymeric flocculation aid is needed.
Example 3 [0191] The following illustrative Example involves the use of a modified calcium carbonate, i.e. the calcium carbonate is not covered by a coating comprising at least one cationic polymer, in combination with a polymeric flocculation aid for the purification of two different sludge samples. Said modified calcium carbonate has a weight medium particle diameter d50 value of 1.6 μίτι (measured according to the sedimentation process) and a specific surface area of 45 m2/g (measured using nitrogen and the BET process), before surface treatment. As the polymeric flocculation aid, the commercially available flocculation aid FLOPAM™ FB 608 (commercially available from SNF Floerger, France) was used.
[0192] The purification process was performed on a mixed sludge (a blend of a primary and biological sludge) sampled from STEP Collombey-Muraz and a digested sludge sampled from STEP AIEE Penthaz. 200 ml of the respective sludge sample was added to a slurry of modified calcium carbonate having a content of surface-treated calcium carbonate of 31.8 wt.-%, based on the total weight of the slurry. After manual agitation, the flocculation was completed by adding the polymeric flocculation aid. The polymeric flocculation aid was used in the form of a suspension having a content of flocculation aid of 0.5 wt.-%, based on the total weight of the suspension. The content of polymeric flocculation aid in the sample was monitored for the respective sludge samples. Tables 5 and 6 summary the details of the utilized amounts of surface-treated calcium carbonate and the measured reduction of polymeric flocculation aid.
Table 5: results for the mixed sludge
Table 6: results for the digested sludge
[0193] During the purification process of the mixed sludge as well as for the digested sludge samples treated with a combination of the modified calcium carbonate and a polymeric flocculation aid, a concentration reduction in the range of 13 to 21 % for the polymeric flocculation aid was obtained.
[0194] Overall, it can be concluded that the use of the modified calcium carbonate in combination with a polymeric flocculation aid has only slight effects on the amounts of polymeric flocculation aid required for complete flocculation, i.e of below 21 %. In contrast thereto, the inventive surface-treated calcium carbonate achieves a reduction of polymeric flocculation aid of up to 79 % compared to the initial concentration.
Example 4 [0195] The following illustrative Example involves the use of different amounts of a surface-treated calcium carbonate in combination with a polymeric flocculation aid for the purification of riverwater. Said surface-treated calcium carbonate comprises a modified calcium carbonate and has a weight medium particle diameter d50 value of 2.0 μίτι (measured according to the sedimentation process) and a specific surface area of 56 m2/g (measured using nitrogen and the BET process), before surface treatment. The surface-treated natural calcium carbonate is covered by a coating comprising poly(diallyldimethylammonium chloride) having a cationic charge density of 6.2 mEq/g. The poly(diallyldimethylammo-nium chloride) is present in the coating in an amount of 1.5 wt.-%, based on the dry weight of the calcium carbonate. As the polymeric flocculation aid, the commercially available flocculation aid Nerolan AG 580 (commercially available from Nerolan Wassertechnik GmbH, Germany) was used. Nerolan AG 580 represents a polyacrylate which is free of acrylamide.
[0196] As a comparative Example, aluminum sulfate in combination with a polyacrylmide as the polymeric flocculation aid was used. As the polymeric flocculation aid, the commercially available flocculation aid Praestol 650 TR (commercially available from Ashland Deutschland GmbH, Germany) was used.
[0197] The purification process was performed on river water of the Neva in Russia sampled from a water barrage. Differing amounts of surface-treated calcium carbonate and 10 ppm of aluminum sulfate, respectively, was added to about 450 ml of the water sample. After agitation at 400 U/min for about 30 s, the flocculation was completed by adding the respective polymeric flocculation aid. Table 7 summaries the details of the utilized amounts of surface-treated calcium carbonate, the utilized amounts of polymeric flocculation aid and the physical and chemical results of purification.
Table 7
(continued)
[0198] Overall, it can be concluded that the use of the surface-treated Calciumcarbonate in combination with a polymeric flocculation aid has a positive effect on the quality of the water obtained by the purification process.
Example 5 [0199] The following illustrative example involves the use of a surface-treated calcium carbonate in combination with a polymeric flocculation aid for the purification of a river wherein said flocculation aid is being added in two portions. Said surface-treated calcium carbonate comprises a modified calcium carbonate and has a weight medium particle diameter d50 value of 2.0 μίτι (measured according to the sedimentation process) and a specific surface area of 56 m1/g (measured using nitrogen and the BET process), before surface treatment. The surface-treated natural calcium carbonate is covered by a coating comprising poly(diallyldimethylammonium chloride) having a cationic charge density of 6.2 mEq/g. The poly(diallyldimethylammonium chloride) is present in the coating in an amount of 1.5 wt.-%, based on the dry weight of the calcium carbonate. As the polymeric flocculation aid, the commercially available flocculation aid Nerolan AG 580 (commercially available from Nerolan Wassertechnik GmbH, Germany) was used. Nerolan AG 580 represents a polyacrylate which is free of acrylamide.
[0200] The purification process was performed on a river sludge sampled from the Elbe near Hamburg, Germany. The solid content of the river sludge was adapted to 17g/L. 45 ppm of the surface-treated calcium carbonate was added to the sludge under stirring conditions of 350 rpm during 5 seconds. The polymeric flocculation aid was added in amounts of 2000 ppm. Addition can be made in one or more portions. The final mixture was allowed to settle for 60 seconds, and was checked by visual inspection.
[0201] The supernatant was clear with no apparent particles visible. Sedimentation showed a proper separation between solid and liquid. Stability of the flocculated sludge was very good and determined as described hereto below. The settled mixture was poured 10x from one beaker glass to another and finally the mixture was filtered over a 200 μίτι sieve. The filtrate was checked by visual inspection. If the filtrate remained clear, the stability of the flocculated sludge is considered as very good. If the filtrate shows to be cloudy then the stability of the flocculated sludge is less stable, depending on the degree of the haze of the filtrate.
Claims 1. Use of a surface-treated calcium carbonate for water purification and/or dewatering of sludges and/or sediments, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer, wherein the surface-treated calcium carbonate comprises surface-modified calcium carbonate that has been processed with cationic polymers through an additional treatment step, and wherein the surface-modified calcium carbonate is obtained by reacting a natural calcium carbonate and/or precipitated calcium carbonate with an acid and with carbon dioxide prior to the preparation of the surface-treated calcium carbonate, wherein the carbon dioxide is formed in situ by the acid treatment and/or is supplied from an external source. 1
The use according to claim 1, wherein the calcium carbonate particles of the at least one surface-treated calcium carbonate has a weight median particle diameter d50 value of between 0.01 μηι and 250 μίτι, preferably between 0.06 μίτι and 225 μίτι, more preferably between 1 μίτι and 200 μίτι, even more preferably between 1 μίτι and 150 μίτι and most preferably between 1 μίτι and 100 μίτι and/or the calcium carbonate particles of the surface-treated calcium carbonate has a specific surface area of from 1 to 250 m1/g, more preferably from 2 to 200 m1/g, even more preferably from 30 to 150 m1/g and most preferably from 30 to 100 m1/g. 3. The use according to any one of claims 1 or2, wherein the coating of the surface-treated calcium carbonate comprises at least one cationic polymer having a positive charge density in the range of 1 mEq/g and 15 mEq/g, more preferably in the range of 2.5 mEq/g and 12.5 mEq/g and most preferably in the range of 5 mEq/g and 10 mEq/g and/or the coating of the surface-treated calcium carbonate comprises at least one cationic polymer in which at least 60 % of the monomer units have a cationic charge, preferably at least 70 %, more preferably at least 80 %, even more preferably at least 90 % and most preferably equal to 100 %. 4. The use according to anyone of claims 1 to 3, wherein the coating of the surface-treated calcium carbonate comprises at least one cationic polymer having a weight average molecular weight Mw of below 1,000,000 g/mole, more preferably from 50,000 to 750,000 g/mole, even more preferably from 50,000 to 650,000 g/mole and most preferably from 100,000 to 300,000 g/mole. 5. The use according to anyone of claims 1 to 4, wherein the coating of the surface-treated calcium carbonate comprises at least one cationic polymer being a homopolymer based on monomer units selected from the group consisting of diallyldialkyl ammonium salts; tertiary and quaternized amines; quaternized imines;, preferably diallyldialkyl ammonium salts. 6. The use according to anyone of claims 1 to 4, wherein the coating of the surface-treated calcium carbonate comprises at least one cationic polymer being a copolymer based on monomer units selected from diallyldialkyl ammonium salts and comonomer units selected from the group consisting of acrylamide; methacrylamide; Ν,Ν-dimethyl acrylamide; acrylic acid; methacrylic acid; vinylsulfonic acid; vinyl pyrrolidone; hydroxyl ethyl acrylate; styrene; methyl methacrylate; vinyl acetate and mixtures thereof. 7. The use according to any one of claims 1 to 6, wherein at least 10 % of the accessible surface area of the calcium carbonate is covered by a coating comprising a cationic polymer, preferably at least 20 % of the accessible surface area, more preferably at least 30 %, even more preferably at least 40 % and most preferably at least 50 % of the accessible surface area. 8. The use according to any one of claims 1 to 7, wherein the surface-treated calcium carbonate is in powder form and/or in the form of granules or in the form of slurry. 9. The use according to anyone of claims 1 to 8, wherein the surface-treated calcium carbonate is used in combination with at least one polymeric flocculation aid. 10. The use according to claim 9, wherein the polymeric flocculation aid has a weight average molecular weight Mw in the range from 100,000 to 10,000,000 g/mole, preferably in the range from 300,000 to 5,000,000 g/mole, more preferably in the range from 300,000 to 1,000,000 g/mole and most preferably in the range from 300,000 to 800,000 g/mole and/or the polymeric flocculation aid is non-ionic or ionic, preferably a cationic or anionic polymer selected from polyacrylamides, polyacrylates, poly(diallyldimethylammonium chloride), polyethyleneimines, polyamines, starches and mixtures thereof. 11. A composite material comprising a surface-treated calcium carbonate and impurities obtainable by a process for the purification ofwaterand/ordewatering of sludges and/or sediments, the process comprising the following steps of a) providing water to be purified and/or sludge and/or sediment to be dewatered comprising impurities b) providing at least one surface-treated calcium carbonate, wherein at least 1 % of the accessible surface area of the calcium carbonate is covered by a coating comprising at least one cationic polymer, and c) contacting the water and/or sludge and/or sediment of step a) with the at least one surface-treated calcium carbonate of step b) for obtaining a composite material of surface-treated calcium carbonate and impurities, wherein the at least one surface-treated calcium carbonate comprises surface-modified calcium carbonate that has been processed with cationic polymers through an additional treatment step, and wherein the surface-modified calcium carbonate is obtained by reacting a natural calcium carbonate and/or precipitated calcium carbonate with an acid and with carbon dioxide prior to the preparation of the surface-treated calcium carbonate, wherein the carbon dioxide is formed in situ by the acid treatment and/or is supplied from an external source. 12. The composite material according to claim 11, wherein the water and/or sludge and/or sediment of step a) is selected from industrial waste water, drinking water, urban waste water, sludge such as harbour sludge, river sludge, coastal sludge or digested sludge, waste water or process water from breweries or other beverage industries, waste water or process water in the paper industry, colour-, paints-, or coatings industry, agricultural waste water, slaughterhouse waste water, leather industry waste water and leather tanning industry. 13. The composite material according to anyone of claims 11 or 12, wherein the calcium carbonate particles of the at least one surface-treated calcium carbonate has a weight median particle diameter d50 value of between 0.01 μηι and 250 μίτι, preferably between 0.06 μίτι and 225 μίτι, more preferably between 1 μίτι and 200 μίτι, even more preferably between 1 μίτι and 150 μίτι and most preferably between 1 μίτι and 100 μίτι and/or the calcium carbonate particles of the at least one surface-treated calcium carbonate has a specific surface area of from 1 to 250 m2/g, more preferably from 20 to 200 m2/g, even more preferably from 30 to 150 m2/g and most preferably from 30 to 100 m2/g. 14. The composite material according to any one of claims 11 to 13, wherein the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer having a positive charge density in the range of 1 mEq/g and 15 mEq/g, more preferably in the range of 2.5 mEq/g and 12.5 mEq/g and most preferably in the range of 5 mEq/g and 10 mEq/g and/or the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer in which at least 60 % of the monomer units have a cationic charge, preferably at least 70 %, more preferably at least 80 %, even more preferably at least 90 % and most preferably equal to 100 %. 15. The composite material according to any one of claims 11 to 14, wherein the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer having a weight average molecular weight Mw of below 1,000,000 g/mole, more preferably from 50,000 to 750,000 g/mole, even more preferably from 50,000 to 650.000 g/mole and most preferably from 100,000 to 300,000 g/mole. 16. The composite material according to any one of claims 11 to 15, wherein the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer being a homopolymer based on monomer units selected from the group consisting of diallyldialkyl ammonium salts; tertiary and quaternized amines; quaternized imines; preferably diallyldialkyl ammonium salts. 17. The composite material according to any one of claims 11 to 15, wherein the coating of the at least one surface-treated calcium carbonate comprises at least one cationic polymer being a copolymer based on monomer units selected from diallyldialkyl ammonium salts and comonomer units selected from the group consisting of acrylamide; methacrylamide; Ν,Ν-dimethyl acrylamide; acrylic acid; methacrylic acid; vinylsulfonic acid; vinyl pyrrolidone; hydroxyl ethyl acrylate; styrene; methyl methacrylate; vinyl acetate and mixtures thereof. 18. The composite material according to any one of claims 11 to 17, wherein at least 10 % of the accessible surface area of the calcium carbonate is covered by a coating comprising a cationic polymer, preferably at least 20 % of the accessible surface area, more preferably at least 30 %, even more preferably at least 40 % and most preferably at least 50 % of the accessible surface area. 19. The composite material according to any one of claims 11 to 18, wherein the at least one surface-treated calcium carbonate is in powder form and/or in the form of granules or in the form of a slurry. 20. The composite material according to any one of claims 11 to 19, wherein the process further comprises step d) of contacting the water to be purified and/or sludge and/or sediment to be dewatered of step a) with at least one polymeric flocculation aid. 21. The composite material according to claim 20, wherein the polymeric flocculation aid has a weight average molecular weight Mw in the range from 100,000 to 10,000,00 g/mole, preferably in the range from 300,000 to 5,000,000 g/mole, more preferably in the range from 300,000 to 1,000,000 g/mole and most preferably in the range from 300,000 to 800.000 g/mole and/or the polymeric flocculation aid is non-ionic or ionic, preferbly a cationic or anionic polymer selected from polyacrylamides, polyacrylates, poly(diallyldimethylammonium chloride), polyethyleneimines, polyamines, starches and mixtures thereof. 22. The composite material according to any one of claims 20 or 21, wherein step c) and step d) are carried out simultaneously or separately, preferably simultaneously. 23. The composite material according to any one of claims 11 to 22, wherein step c) and/or step d) are carried out by at least partially covering the surface of the water and/or sludge and/or sediment to be treated of step a) with the at least one surface-treated calcium carbonate of step b) and/or mixing the water and/or sludge and/or sediment to be treated of step a) with the at least one surface-treated calcium carbonate of step b). 24. The composite material according to any one of claims 11 to 23, wherein step c) and/or step d) are repeated one or more times. 25. The composite material according to any one of claims 11 to 24, wherein the composite material of the at least one surface-treated calcium carbonate and impurities is removed from the water and/or sludge and/or sediment phase by filtration, sedimentation and/or centrifugation.
Patentansprüche 1. Verwendung eines oberflächenbehandelten Calciumcarbonats zur Reinigung von Wasser und/oder zum Entwässern von Schlämmen und/oder Sedimenten, wobei wenigstens 1 % der zugänglichen Oberfläche des Calciumcarbonats durch eine Beschichtung, die wenigstens ein kationisches Polymer umfasst, bedeckt ist, wobei das oberflächenbehandelte Calciumcarbonat oberflächenmodifiziertes Calciumcarbonat umfasst, welches mit kationischen Polymeren durch einen zusätzlichen Behandlungsschritt verarbeitet wurde, und wobei das oberflächenmodifizierte Calciumcarbonat erhalten wird durch die Umsetzung eines natürlichen Calciumcarbonats und/oder gefällten Calciumcarbonats mit einer Säure und mit Kohlenstoffdioxid vor der Herstellung des oberflächenbehandelten Calciumcarbonats, wobei das Kohlenstoffdioxid in situ durch die Säurebehandlung gebildet wird und/oder aus einer externen Quelle zugeführt wird. 2. Verwendung nach Anspruch 1, bei der die Calciumcarbonatpartikel des wenigstens einen oberflächenbehandelten Calciumcarbonats einen gewichtsgemittelten Partikeldurchmesser d50- Wert zwischen 0,01 μίτι und 250 μίτι aufweisen, bevorzugt zwischen 0,06 μίτι und 225 μίτι, bevorzugterzwischen 1 μίτι und 200 μίτι, noch bevorzugter zwischen 1 μίτι und 150 μίτι, und am meisten bevorzugt zwischen 1 μίτι und 100 μίτι, und/oder die Calciumcarbonatpartikel des wenigstens einen oberflächenbehandelten Calciumcarbonats weisen eine spezifische Oberfläche von 1 bis 250 m2/g auf, bevorzugter von 2 bis 200 m2/g, noch bevorzugter von 30 bis 150 m2/g, und am meisten bevorzugt von 30 bis 100 m2/g. 3. Verwendung nach einem der Ansprüche 1 oder 2, bei der die Beschichtung des oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer mit einer positiven Ladungsdichte im Bereich von 1 mEq/g und 15 mEq/g umfasst, bevorzugter im Bereich von 2,5 mEq/g und 12,5 mEq/g, und am meisten bevorzugt im Bereich von 5 mEq/g und 10 mEq/g, und/oder die Beschichtung des oberflächenbehandelten Calciumcarbonats umfasst wenigstens ein kationisches Polymer, bei dem wenigstens 60 % der Monomer-Einheiten eine kationische Ladung aufweisen, bevorzugt wenigstens 70 %, bevorzugter wenigstens 80 %, noch bevorzugter wenigstens 90 %, und am meisten bevorzugt gleich 100 %. 4. Verwendung nach einem der Ansprüche 1 bis 3, bei der die Beschichtung des oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer mit einem gewichtsgemittelten Molekulargewicht Mw von unter 1 000 000 g/mol umfasst, bevorzugter von 50 000 bis 750 000 g/mol, noch bevorzugter von 50 000 bis 650 000 g/mol, und am meisten bevorzugt von 100 000 bis 300 000 g/mol. 5. Verwendung nach einem der Ansprüche 1 bis 4, bei der die Beschichtung des oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer umfasst, welches ein Homopolymer ist, basierend auf Monomer-Einheiten ausgewählt aus der Gruppe bestehend aus Diallylammoniumsalzen, tertiären oder quaternären Aminen, quaternären Iminen, bevorzugt Diallylammoniumsalzen. 6. Verwendung nach einem der Ansprüche 1 bis 4, bei der die Beschichtung des oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer umfasst, welches ein Copolymer ist, basierend auf Monomer-Einheiten ausgewählt aus Diallylammoniumsalzen, und Comonomer-Einheiten ausgewählt aus der Gruppe bestehend aus Acrylamid, Methacrylamid, Ν,Ν-Dimethylacrylamid, Acrylsäure, Methacrylsäure, Vinylsulfonsäure, Vinylpyrro-lidon, Hydroxyethylacrylat, Styrol, Methylmethacrylat, Vinylacetat sowie Gemischen davon. 7. Verwendung nach einem der Ansprüche 1 bis 6, bei der wenigstens 10 % der zugänglichen Oberfläche des Calciumcarbonats durch eine Beschichtung, die ein kationisches Polymer umfasst, bedeckt ist, bevorzugt wenigstens 20 % der zugänglichen Oberfläche, bevorzugter wenigstens 30 % der zugänglichen Oberfläche, noch bevorzugter wenigstens 40 % der zugänglichen Oberfläche, und am meisten bevorzugt wenigstens 50 % der zugänglichen Oberfläche. 8. Verwendung nach einem der Ansprüche 1 bis 7, bei der das oberflächenbehandelte Calciumcarbonat in Pulverform und/oder in der Form von Granulaten oder in der Form einer Aufschlämmung ist. 9. Verwendung nach einem der Ansprüche 1 bis 8, bei derdas oberflächenbehandelte Calciumcarbonat in Kombination mit wenigstens einem polymeren Flockungshilfsmittel verwendet wird. 10. Verwendung nach Anspruch 9, bei derdas polymere Flockungshilfsmittel ein gewichtsgemitteltes Molekulargewicht Mw im Bereich von 100 000 bis 10 000 000 g/mol aufweist, bevorzugt im Bereich von 300 000 bis 5 000 000 g/mol, bevorzugter im Bereich von 300 000 bis 1 000 000 g/mol, und am meisten bevorzugt im Bereich von 300 000 bis 800 000 g/mol, und/oder das polymere Flockungshilfsmittel ist ein nichtionisches oder ionisches, bevorzugt ein kationisches oder anionisches Polymer, ausgewählt aus Polyacrylamiden, Polyacrylaten, Polydiallyldimethylammo-niumchlorid, Polyethyleniminen, Polyaminen, Stärken und Gemischen davon. 11. Kompositmaterial, umfassend ein oberflächenbehandeltes Calciumcarbonat und Verunreinigungen, erhältlich durch ein Verfahren zur Reinigung von Wasser und/oder zum Entwässern von Schlämmen und/oder Sedimenten, umfassend die folgenden Schritte: a) Bereitstellen von zu reinigendem Wasser und/oder von zu entwässerndem Schlamm und/oder Sediment, umfassend Verunreinigungen; b) Bereitstellen von wenigstens einem oberflächenbehandelten Calciumcarbonat, wobei wenigstens 1 % der zugänglichen Oberfläche des Calciumcarbonats durch eine Beschichtung, die wenigstens ein kationisches Polymer umfasst, bedeckt ist, und c) Inkontaktbringen des Wassers und/oder des Schlamms und/oder des Sediments aus Schritt a) mit dem wenigstens einen oberflächenbehandelten Calciumcarbonat aus Schritt b) zum Erhalten eines Kompositmate-rials aus oberflächenbehandeltem Calciumcarbonat und Verunreinigungen, wobei das wenigstens eine oberflächenbehandelte Calciumcarbonat ein oberflächenmodifiziertes Calciumcarbonat umfasst, welches mit kationischen Polymeren durch einen zusätzlichen Behandlungsschritt verarbeitet wurde, wobei das oberflächenmodifizierte Calciumcarbonat erhalten wird durch die Umsetzung eines natürlichen Calciumcarbonats und/oder gefällten Calciumcarbonats mit einer Säure und mit Kohlenstoffdioxid vor der Herstellung des oberflächenbehandelten Calciumcarbonats, wobei das Kohlenstoffdioxid in situ durch die Säurebehandlung gebildet wird und/oder aus einer externen Quelle zugeführt wird. 12. Kompositmaterial nach Anspruch 11, bei dem das Wasser und/oder der Schlamm und/oder das Sediment aus Schritt a) ausgewählt ist aus Industrieabwasser, Trinkwasser, kommunalem Abwasser, Schlamm, wie Hafenschlamm, Flussschlamm, Küstenschlamm oder Faulschlamm, Abwasser oder Nutzwasser aus Brauereien oder anderen Getränkeindustrien, Abwasser oder Nutzwasser in der Papierindustrie, Farbstoff-, Färb- oder Beschichtungsindustrie, Abwasser aus der Landwirtschaft, Schlachthausabwasser, Abwasser aus der Lederindustrie und der Ledergerbungsindustrie. 13. Kompositmaterial nach einem der Ansprüche 11 oder 12, bei dem die Calciumcarbonatpartikel des wenigstens einen oberflächenbehandelten Calciumcarbonats einen gewichtsgemittelten Partikeldurchmesser d50-Wert zwischen 0,01 μίτι und 250 μίτι aufweisen, bevorzugt zwischen 0,06 μίτι und 225 μίτι, bevorzugterzwischen 1 μίτι und 200 μίτι, noch bevorzugterzwischen 1 μίτι und 150 μίτι, und am meisten bevorzugt zwischen 1 μίτι und 100 μίτι, und/oder die Calciumcarbonatpartikel des wenigstens einen oberflächenbehandelten Calciumcarbonats weisen eine spezifische Oberfläche von 1 bis 250 m2/g auf, bevorzugter von 20 bis 200 m2/g, noch bevorzugter von 30 bis 150 m2/g, und am meisten bevorzugt von 30 bis 100 m2/g. 14. Kompositmaterial nach einem der Ansprüche 11 bis 13, bei dem die Beschichtung des wenigstens einen oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer mit einer positiven Ladungsdichte im Bereich von 1 mEq/g und 15 mEq/g umfasst, bevorzugter im Bereich von 2,5 mEq/g und 12,5 mEq/g, und am meisten bevorzugt im Bereich von 5 mEq/g und 10 mEq/g, und/oder die Beschichtung des wenigstens einen oberflächenbehandelten Calciumcarbonats umfasst wenigstens ein kationisches Polymer, bei dem wenigstens 60 % der Monomer-Einheiten eine kationische Ladung aufweisen, bevorzugt wenigstens 70 %, bevorzugter wenigstens 80 %, noch bevorzugter wenigstens 90 %, und am meisten bevorzugt gleich 100 %. 15. Kompositmaterial nach einem der Ansprüche 11 bis 14, bei dem die Beschichtung des wenigstens einen oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer mit einem gewichtsgemittelten Molekulargewicht Mw von unter 1 000 000 g/mol umfasst, bevorzugter von 50 000 bis 750 000 g/mol, noch bevorzugter von 50 000 bis 650 000 g/mol, und am meisten bevorzugt von 100 000 bis 300 000 g/mol. 16. Kompositmaterial nach einem der Ansprüche 11 bis 15, bei dem die Beschichtung des wenigstens einen oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer umfasst, welches ein Homopolymer ist, basierend auf Monomer-Einheiten ausgewählt aus der Gruppe bestehend aus Diallylammoniumsalzen, tertiären oder quaternären Aminen, quaternären Iminen, bevorzugt Diallylammoniumsalzen. 17. Kompositmaterial nach einem der Ansprüche 11 bis 15, bei dem die Beschichtung des wenigstens einen oberflächenbehandelten Calciumcarbonats wenigstens ein kationisches Polymer umfasst, welches ein Copolymer ist, basierend auf Monomer-Einheiten ausgewähltaus Diallylammoniumsalzen, und Comonomer-Einheiten ausgewählt aus der Gruppe bestehend aus Acrylamid, Methacrylamid, Ν,Ν-Dimethylacrylamid, Acrylsäure, Methacrylsäure, Vinylsulfonsäure, Vinylpyrrolidon, Hydroxyethylacrylat, Styrol, Methylmethacrylat, Vinylacetat sowie Gemischen davon. 18. Kompositmaterial nach einem der Ansprüche 11 bis 17, bei dem wenigstens 10 % der zugänglichen Oberfläche des Calciumcarbonats durch eine Beschichtung, die ein kationisches Polymer umfasst, bedeckt ist, bevorzugt wenigstens 20 % der zugänglichen Oberfläche, bevorzugter wenigstens 30 % der zugänglichen Oberfläche, noch bevorzugter wenigstens 40 % der zugänglichen Oberfläche, und am meisten bevorzugt wenigstens 50 % der zugänglichen Oberfläche. 19. Kompositmaterial nach einem der Ansprüche 11 bis 18, bei dem das wenigstens eine oberflächenbehandelte Calciumcarbonat in Pulverform und/oder in der Form von Granulaten oder in der Form einer Aufschlämmung ist. 20. Kompositmaterial nach einem der Ansprüche 11 bis 19, bei dem das Verfahren ferner einen Schritt d) umfasst, bei dem das zu reinigende Wasser und/oder der zu entwässernde Schlamm und/oder das zu entwässernde Sediment aus Schritt a) mit wenigstens einem polymeren Flockungshilfsmittel in Kontakt gebracht wird. 21. Kompositmaterial nach Anspruch 20, bei dem das polymere Flockungshilfsmittel ein gewichtsgemitteltes Molekulargewicht Mw im Bereich von 100 000 bis 10 000 000 g/mol aufweist, bevorzugt im Bereich von 300 000 bis 5 000 000 g/mol, bevorzugter im Bereich von 300 000 bis 1 000 000 g/mol, und am meisten bevorzugt im Bereich von 300 000 bis 800 000 g/mol, und/oder das polymere Flockungshilfsmittel ist ein nichtionisches oder ionisches, bevorzugt ein kationisches oder anionisches Polymer, ausgewählt aus Polyacrylamiden, Polyacrylaten, Polydiallyldi-methylammoniumchlorid, Polyethyleniminen, Polyaminen, Stärken und Gemischen davon. 22. Kompositmaterial nach einem der Ansprüche 20 oder 21, bei dem Schritt c) und Schritt d) gleichzeitig oder getrennt ausgeführt werden, bevorzugt gleichzeitig. 23. Kompositmaterial nach einem der Ansprüche 11 bis 22, bei dem Schritt c) und/oder Schritt d) ausgeführt werden durch wenigstens teilweises Bedecken der Oberfläche des zu behandelnden Wassers und/oder Schlamms und/oder Sediments aus Schritt a) mit dem wenigstens einen oberflächenbehandelten Calciumcarbonat aus Schritt b), und/oder durch Vermischen des zu behandelnden Wassers und/oder Schlamms und/oder Sediments aus Schritt a) mit dem wenigstens einen oberflächenbehandelten Calciumcarbonat aus Schritt b). 24. Kompositmaterial nach einem der Ansprüche 11 bis 23, bei dem Schritt c) und/oder Schritt d) ein oder mehrmals wiederholt werden. 25. Kompositmaterial nach einem der Ansprüche 11 bis 24, bei dem das Kompositmaterial aus dem wenigstens einen oberflächenbehandelten Calciumcarbonat und Verunreinigungen aus der Wasser- und/oder Schlamm- und/oder Sedimentphase durch Filtration, Sedimentation und/oder Zentrifugation entfernt wird.
Revendications 1. Utilisation d’un carbonate de calcium traité en surface pour la purification d’eau et/ou la déshydratation de boues et/ou de sédiments, dans laquelle au moins 1 % de la surface accessible du carbonate de calcium est recouvert par un revêtement comprenant au moins un polymère cationique, dans laquelle le carbonate de calcium traité en surface comprend un carbonate calcium modifié en surface qui a été traité avec des polymères cationiques par le biais d’une étape de traitement supplémentaire, et dans laquelle le carbonate de calcium modifié en surface est obtenu en faisant réagir un carbonate de calcium naturel et/ou un carbonate de calcium précipité avec un acide et avec du dioxyde de carbone avant la préparation du carbonate de calcium traité en surface, le dioxyde de carbone étant formé in situ par le traitement acide et/ou provenant d’une source externe. 2. Utilisation selon la revendication 1, dans laquelle les particules de carbonate de calcium d’au moins un carbonate de calcium traité en surface ont un diamètre de particule médian en poids d50 compris entre 0,01 μηι et 250 μίτι, de préférence entre 0,06 μίτι et 225 μίτι, plus préférablement entre 1 μίτι et 200 μίτι, encore plus préférablement entre 1 μίτι et 150 μίτι et de manière préférée entre toutes entre 1 μίτι et 100 μίτι et/ou les particules de carbonate de calcium d’au moins un carbonate de calcium traité en surface ont une surface spécifique de 1 à 250 m2/g, plus préférablement de 2 à 200 m2/g, encore plus préférablement de 30 à 150 m2/g et de manière préférée entre toutes de 30 à 100 m2/g. 3. Utilisation selon la revendication 1 ou 2, dans laquelle le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique ayant une densité de charge positive dans la plage comprise entre 1 mEq/g et 15 mEq/g, plus préférablement dans la plage comprise entre 2,5 mEq/g et 12,5 mEq/g et de manière préférée entre toutes dans la plage comprise entre 5 mEq/g et 10 mEq/g et/ou le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique dans lequel au moins 60 % des motifs monomères ont une charge cationique, de préférence au moins 70 %, plus préférablement au moins 80 %, encore plus préférablement au moins 90 % et de manière préférée entre toutes 100 %. 4. Utilisation selon l’une quelconque des revendications 1 à 3, dans laquelle le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique ayant un poids moléculaire moyen en masse Mw inférieur à 1 OOOOOOg/mole, plus préférablementde50 000à750 000g/mole, encore plus préférablement de 50 000 à 650 000 g/mole et de manière préférée entre toutes de 100 000 à 300 000 g/mole. 5. Utilisation selon l’une quelconque des revendications 1 à 4, dans laquelle le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique qui est un homopolymère basé sur des motifs monomères choisis dans le groupe constitué par les sels de diallyldialkylammonium ; les amines tertiaires et quaternisées ; les imines quaternisées, de préférence les sels de diallyldialkylammonium. 6. Utilisation selon l’une quelconque des revendications 1 à 4, dans laquelle le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique qui est un copolymère basé sur des motifs monomères choisis parmi les sels de diallyldialkylammonium et des motifs comonomères choisis dans le groupe constitué par l’acrylamide ; le méthacrylamide ; le Ν,Ν-diméthylacrylamide ; l’acide acrylique ; l’acide méthacrylique ; l’acide vinylsulfonique ; la vinylpyrrolidone ; l’acrylate d’hydroxyéthyle ; le styrène ; le méthacrylate de méthyle ; l’acétate de vinyle et leurs mélanges. 7. Utilisation selon l’une quelconque des revendications 1 à 6, dans laquelle au moins 10 % de la surface accessible du carbonate de calcium sont recouverts d’un revêtement comprenant un polymère cationique, de préférence au moins 20 % de la surface accessible, plus préférablement au moins 30 %, encore plus préférablement au moins 40 % et de manière préférée entre toutes au moins 50 % de la surface accessible. 8. Utilisation selon l’une quelconque des revendications 1 à 7, dans laquelle le carbonate de calcium traité en surface est sous forme de poudre et/ou sous forme de granules ou sous forme de suspension. 9. Utilisation selon l’une quelconque des revendications 1 à 8, dans laquelle le carbonate de calcium traité en surface est utilisé dans une combinaison avec au moins un agent de floculation polymère. 10. Utilisation selon la revendication 9, dans laquelle l’agent de floculation polymère a un poids moléculaire moyen en masse Mw compris dans la plage allant de 100 000 à 10 000 000 g/mole, de préférence dans la plage allant de 300 000 à 5 000 000 g/mole, plus préférablement dans la plage allant de 300 000 à 1 000 000 g/mole et de manière préférée entre toutes dans la plage allant de 300 000 à 800 000 g/mole et/ou l’agent de floculation polymère est non ionique ou ionique, de préférence un polymère cationique ou anionique choisi parmi les polyacrylamides, les poly acrylates, les poly(chlorure de diallyldiméthylammonium),les polyéthylène-imines, les polyamines, les amidons et leurs mélanges. 11. Matériau composite comprenant un carbonate de calcium traité en surface et des impuretés pouvant être obtenu par un procédé de purification d’eau et/ou de déshydratation de boues et/ou de sédiments, le procédé comprenant les étapes suivantes consistant à : a) fournir une eau à purifier et/ou une boue et/ou un sédiment à déshydrater comprenant des impuretés ; b) fournir au moins un carbonate de calcium traité en surface, au moins 1 % de la surface accessible du carbonate de calcium étant recouvert par un revêtement comprenant au moins un polymère cationique ; et c) mettre en contact l’eau et/ou la boue et/ou le sédiment de l’étape a) avec au moins un carbonate de calcium traité en surface de l’étape b) pour obtenir un matériau composite de carbonate de calcium traité en surface et des impuretés, au moins un carbonate de calcium traité en surface comprenant un carbonate calcium modifié en surface qui a été traité avec des polymères cationiques parle biais d’une étape de traitement supplémentaire, dans lequel le carbonate de calcium modifié en surface est obtenu en faisant réagir un carbonate de calcium naturel et/ou un carbonate de calcium précipité avec un acide et avec du dioxyde de carbone avant la préparation du carbonate de calcium traité en surface, le dioxyde de carbone étant formé in situ par le traitement acide et/ou provenant d’une source externe. 12. Matériau composite selon la revendication 11, dans lequel l’eau et/ou la boue et/ou le sédiment de l’étape a) est choisi parmi les eaux usées industrielles, une eau potable, les eaux usées urbaines, une boue telle qu’une boue portuaire, une boue de rivière, une boue côtière ou une boue digérée, les eaux usées ou l’eau d’un procédé provenant de brasseries ou d’autres industries de boissons, les eaux usées ou l’eau d’un procédé provenant de l’industrie du papier, de l’industrie des couleurs, des peintures ou des revêtements, les eaux usées agricoles, les eaux usées d’abattoirs, les eaux usées de l’industrie du cuir et de l’industrie du tannage du cuir. 13. Matériau composite selon la revendication 11 ou 12, dans lequel les particules de carbonate de calcium d’au moins un carbonate de calcium traité en surface ont un diamètre de particule médian en poids d50 compris entre 0,01 μίτι et 250 μίτι, de préférence entre 0,06 μίτι et 225 μίτι, plus préférablement entre 1 μίτι et 200 μίτι, encore plus préférablement entre 1 μίτι et 150 μίτι et de manière préférée entre toutes entre 1 μίτι et 100 μίτι et/ou les particules de carbonate de calcium d’au moins un carbonate de calcium traité en surface ont une surface spécifique de 1 à 250 m2/g, plus préférablement de 20 à 200 m2/g, encore plus préférablement de 30 à 150 m2/g et de manière préférée entre toutes de 30 à 100 m2/g. 14. Matériau composite selon l’une quelconque des revendications 11 à13, dans lequel le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique ayant une densité de charge positive dans la plage comprise entre 1 mEq/g et 15 mEq/g, plus préférablement dans la plage comprise entre 2,5 mEq/g et 12,5 mEq/g et de manière préférée entre toutes dans la plage comprise entre 5 mEq/g et 10 mEq/g et/ou le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique dans lequel au moins 60 % des motifs monomères ont une charge cationique, de préférence au moins 70 %, plus préférablement au moins 80 %, encore plus préférablement au moins 90 % et de manière préférée entre toutes 100 %. 15. Matériau composite selon l’une quelconque des revendications 11 à 14, dans lequel le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique ayant un poids moléculaire moyen en masse Mw inférieur à 1 000 000 g/mole, plus préférablement de 50 000 à 750 000 g/mole, encore plus préférablement de 50 000 à 650 000 g/mole et de manière préférée entre toutes de 100 000 à 300 000 g/mole. 16. Matériau composite selon l’une quelconque des revendications 11 à 15, dans lequel le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique qui est un homopolymère basé sur des motifs monomères choisis dans le groupe constitué par les sels de diallyldialkylammonium ; les amines tertiaires et quaternisées ; les imines quaternisées, de préférence les sels de diallyldialkylammonium. 17. Matériau composite selon l’une quelconque des revendications 11 à15, dans lequel le revêtement d’au moins un carbonate de calcium traité en surface comprend au moins un polymère cationique qui est un copolymère basé sur des motifs monomères choisis parmi les sels de diallyldialkylammonium et des motifs comonomères choisis dans le groupe constitué par l’acrylamide ; le méthacrylamide ; le Ν,Ν-diméthylacrylamide ; l’acide acrylique ; l’acide méthacrylique ; l’acide vinylsulfonique ; la vinylpyrrolidone ; l’acrylate d’hydroxyéthyle ; le styrène ; le méthacrylate de méthyle ; l’acétate de vinyle et leurs mélanges. 18. Matériau composite selon l’une quelconque des revendications 11 à 17, dans lequel au moins 10 % de la surface accessible du carbonate de calcium sont recouverts d’un revêtement comprenant un polymère cationique, de préférence au moins 20 % de la surface accessible, plus préférablement au moins 30 %, encore plus préférablement au moins 40 % et de manière préférée entre toutes au moins 50 % de la surface accessible. 19. Matériau composite selon l’une quelconque des revendications 11 à 18, dans lequel au moins un carbonate de calcium traité en surface est sous forme de poudre et/ou sous forme de granules ou sous forme de suspension. 20. Matériau composite selon l’une quelconque des revendications 11 à 19, dans lequel le procédé comprend en outre une étape d) consistant à mettre en contact l’eau à purifier et/ou la boue et/ou le sédiment à déshydrater de l’étape a) avec au moins un agent de floculation polymère. 21. Matériau composite selon la revendication 20, dans lequel l’agent de floculation polymère a un poids moléculaire moyen en masse Mw compris dans la plage allant de 100 000 à 10 000 000 g/mole, de préférence dans la plage allant de 300 000 à 5 000 000 g/mole, plus préférablement dans la plage allant de 300 000 à 1 000 000 g/mole et de manière préférée entre toutes dans la plage allant de 300 000 à 800 000 g/mole et/ou l’agent de floculation polymère est non ionique ou ionique, de préférence un polymère cationique ou anionique choisi parmi les polyacrylamides, les polyacrylates, les poly(chlorure de diallyldiméthylammonium),les polyéthylèneimines, les polyami-nes, les amidons et leurs mélanges. 22. Matériau composite selon l’une quelconque des revendications 20 à 21, dans lequel l’étape c) et l’étape d) sont réalisées simultanément ou séparément, de préférence simultanément. 23. Matériau composite selon l’une quelconque des revendications 11 à 22, dans lequel l’étape c) et/ou l’étape d) sont réalisées par revêtement au moins partiel de la surface de l’eau et/ou de la boue et/ou du sédiment à traiter de l’étape a) avec au moins un carbonate de calcium traité en surface de l’étape b) et/ou mélange de l’eau et/ou de la boue et/ou du sédiment à traiter de l’étape a) avec au moins un carbonate de calcium traité en surface de l’étape b). 24. Matériau composite selon l’une quelconque des revendications 11 à 23, dans lequel l’étape c) et/ou l’étape d) sont répétées une ou plusieurs fois. 25. Matériau composite selon l’une quelconque des revendications 11 à 24, dans lequel le matériau composite d’au moins un carbonate de calcium traité en surface et d’impuretés est éliminé de la phase d’eau et/ou de boue et/ou de sédiment par filtration, sédimentation et/ou centrifugation.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description • EP 0273335 A [0009] · WO 0039222 A [0074] • CA 2734310 [0009] · WO 2004083316 A [0074] • US 20060273039 A1 [0009] · WO 2005121257 A [0074] • EP 20111766 A1 [0009] · WO 2009074492 A [0074] • EP 1982759 A1 [0009] · EP 2264108 A1 [0074] [0075] • EP 1974807 A1 [0009] · EP 2264109 A1 [0074] [0075] • EP 1974806 A1 [0009] · US 20090270543 A1 [0096] [0158] • EP 1493716 A1 [0009]
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Claims (10)

Pelöktteelí kaletum-karböuái alkalmazása víztisztításra és iszapok és üledékek vízmentesítésére, és « kapott kompoz! t anyag SZABADALMI IGÉNYPONTOK L FeliLetkezolé kalciœi-karbonâï alkalmazása víztisztításra és/vagy iszapok és/vagy üledékek vlzmentesífösere, ahol a kakíom-karfeotiát elérbetö Müleíi területének legalább 1 a legalább egy kationé® polimert tartalmazó bevonatta! van iedve, aW a Mulelkezdi kalcium-karbonát fölileímödositott kalcium-karbonátot tartalmaz, mely egy további kezelési lépésben kaíionos polimerrel lett kezdve, és ahol a fölületmódosítoít kaleiam-karbonáiot a felületkezelt kalcium-karbonát előállítása előtt természetei kalcium-karbonát és/vagy kicsapott kalcium-karbonát savval és széndioxiddal való reagílföiása: #fán nyerjük, aboil a széndioxid &amp; savas kezeléskor in situ képződik vagy külső förrásbél van betáplálva,Use of diatomaceous caletum carbohydrates for water purification and dewatering of sludges and sediments, and «obtained composite! t material APPLICATIONS OF LABELS L FeliLetkezolé calcium carbonate for water purification and / or descaling of sludges and / or sediments, where at least one of the Myli region of the cocomyl carfate is coated with at least one cationic polymer! there is a perception that the Mulelkezd calcium carbonate contains a labeled calcium carbonate, which, in a further treatment step, starts with a ionic polymer, and wherein the surface-modified kaleiam carbonate is naturally calcium carbonate and / or precipitated calcium carbonate prior to the preparation of the surface-treated calcium carbonate. Reaction with acid and carbon dioxide: # tree, aboil carbon dioxide &amp; in the case of acid treatment, it is formed in situ or an external bleed is fed, 2, Az 1, igénypont; szerinti alkalmazás, ahol a legalább egy felületkezelt kalcium-karbonát szemcséinek d?y átlagos részeeskeátméröje 0,01 pm és 250 um közötti érték, előnyösen 0,06 ptmés 225 pm közötti, előnyösebben Ipm és 200 tun, még előnyösebben 1 pm és ISO pm és MM) pm közöm, és legelőnyösebben 1 pm és 100 pm közötti és/vagy a .felületkezelt kalcium-karbonát szemcsék fajlagos föíüíete 1 -2S0: m~fg, még előnyösebben 2-200 m2% még előnyösebben 30-150 m2/g és legelőnyösebben 30-100 ml/g.2, Claim 1; wherein the mean particle diameter of the particles of the at least one surface treated calcium carbonate is between 0.01 and 250 µm, preferably between 0.06 µm and 225 µm, more preferably between 1 µm and 200 hr, more preferably between 1 µm and ISO pm, and And most preferably between 1 µm and 100 µm and / or the specific surface area of the surface treated calcium carbonate particles is 1 -2 S0: m ~ fg, more preferably 2 to 200 m 2%, more preferably 30 to 150 m 2 / g and most preferably 30-100 ml / g. 3, Az 1. vagy 2. igénypont bármelyike szerinti alkalmazás, ahol a föliieikezelt kalcium-karbonát bevonata magában foglal legalább egy kationos polimert, mellek töltés sűrűsége 1 mEq/g és 15 mEq/g közötti, előnyösebben 2,5 mEq/g és 12,5 mEq/g közötti, es legelőnyösebben 5 mEq.'g és 10 mEq/g közötti és/vagy a fölülétkezelt kaicintn-karbonát bevonat tartalmaz legalább egy kationos polimert, amelyben a monomer egységek legalább 60%~a. előnyösen legalább 70%-a, előnyösebben legalább 80%~a, meg előnyösebben legalább 90%-a, és legelőnyösebben 100%-a kationos töltéssel rendelkezik,The use according to any one of claims 1 or 2, wherein the coating of the calcium-carbonate coated with the overlay comprises at least one cationic polymer, the filling density of the breasts ranging from 1 mEq / g to 15 mEq / g, more preferably 2.5 mEq / g and 12 , 5 mEq / g, and most preferably 5 mEq.g and 10 mEq / g and / or the over-treated kaicinton carbonate coating comprises at least one cationic polymer in which the monomer units are at least 60%. preferably at least 70%, more preferably at least 80%, more preferably at least 90%, and most preferably 100% cationic charge, 4, Az 1-3, igénypontok bármelyike szerinti alkalmazás, ahol a Miletkezelt kalcium-karboííái bevonata legalább egy olyan kationos polimert tartalmaz, melynek M>* átlagos molekulatömege I 000 000 g mol alatti előnyösen 50 000-750 ÖQÖ g/moi még előnyösebben 50 000-650 000 g/moi, és legelőnyösebben 100 000-300 000 g/motThe use according to any one of claims 1-3, wherein the Miletreated calcium carbonate coating comprises at least one cationic polymer having an average molecular weight <RTI ID = 0.0> M> * </RTI> of less than 50,000-750 g / mol, more preferably 50,000-750 mol / mol. 000-650,000 g / moi, and most preferably 100,000-300,000 g / mot 5, Az 1-4, if^j^öafok.Mrmeiyik« szerinti alkalmazás, ahol a feliiktkezeît .kaîetea-fcarborsát bevoaaîa tartalmaz legalább egy kationos polimert, amely a üiallil-diaifeil smraèm- sók; tercier és kvaiernlzált amiook; kvatemizált imiaek; előnyösei disllií-dblki! armnőai-um sók csoportból kiválasztott' monomer egységeken alapuló homopolimer,The use according to any one of claims 1 to 4, wherein the carboxylate is comprised of at least one cationic polymer which is allyl diafilic acid; tertiary and quaternary amides; quatemized imes; prefer disllix-dblki! a homopolymer based on a monomer unit selected from the group consisting of Armnose salts; 6, Az 1-4. igénypontok Mtmelyike szerinti alkalmazás, áltól a felöletkezel kalcium-karbonát bevonata tartalmaz legalább egy olyan kationon polimert, mely egy olyas kopolimer, amely a diallil-díalkíl ammMmm sók közöl választott monomer egységeken, és az akrilarmd; meiateilsmid; RN-dimetl-akrliamid; akrítsav; metakrilsav; vimlszidfensav; vlnllpitFolldan; bldroxiketil-akrilát; szítról; metii-metakriláí; vmil-aeeíáí és ezek keverékei csoportból választóit komooomer egysegeken alapul.6, 1-4. The use according to any one of claims 1 to 3, wherein the coating of calcium carbonate of the topcoat comprises at least one cationic polymer which is a copolymer selected from monomer units selected from diallylalkyl ammonium salts and acrylic resin; meiateilsmid; RN-dimethylamine were akrliamid; akrítsav; methacrylic acid; vimlszidfensav; vlnllpitFolldan; bldroxiketil acrylate; szítról; methyl methacrylate; vmylase and mixtures thereof are selected from the group of comooomer units. 7, Az 1-6-, Igénypontok bármelyike szerinti alkalmazás, ahol a kalcium-karbonát elérhető felületének legalább 1.0%-a, előnyösen az elérhető Miiét legalább 20%m, előnyösebben legalább 30%-a, még előnyösebben legalább 40%-a.és legelőnyösebben legalább 5Ö%~aa kationos polimert tartalmazó bevonattal van fedve,Use according to any one of claims 1-6, wherein at least 1.0% of the available surface area of calcium carbonate, preferably at least 20% m, more preferably at least 30%, more preferably at least 40%, is available. and most preferably at least 5% by weight of the coating comprising a cationic polymer, 8, Az 1-7. igénypontok bármelyike szerinti alkalmazás, ahol a felületkezelt kalcium-karbonát por es/vagy granulátumok vagy zagy tormáiéban vau, Ö, Az 1-8, igénypontok bármelyike szerinti alkalmazás, ahol a felületkezelt kalcium-karbonátot legalább egy polimer flokkuláló szer segédanyaggal kombinációban alkalmazzuk, 10, A 9, igénypont szerinti alkalmazás* ahol a polimer ílokkuiáló szer segédanyag M*< átlagos molekulatömege 100 000-10 Oöö 000 g/mol, előnyösen 300 Ö0Ö-500(1 Ô00 g/moL még előnyösebben 300 000-1 OÖO OOö g/mol és legelőnyösebben 300 OOÜ-kOO 0OÖ g/mok és/vagy a polimer ílokkuiáló szer segédanyag nem-ionos vagy ionos, előnyösen kstionos: vagy amonos polimer, a poli akri Iám Idők, poíiakriJátök, poliCdiallil-dímetil-anmmmnm-klorid), polktiéíMmkek,'poliíiminok, keményítők és ezek keveréket közül kiválasztva.8, 1-7. The use according to any one of claims 1 to 8, wherein the surface treated calcium carbonate powder or granules or slurry is used in the process according to any one of claims 1 to 8, wherein the surface treated calcium carbonate is used in combination with at least one polymeric flocculant excipient 10, Use according to claim 9, wherein the polymer molecular agent adjuvant has an average molecular weight of M * <RTI ID = 0.0> 100kg </RTI> of 100 g / mol, preferably 300 of 500 (preferably 1 to 100 g / mol, more preferably 300,000 to 1 ou g / mol). and most preferably 300 OO-COO OO / g and / or the polymeric excipient excipient is non-ionic or ionic, preferably Kstionic: or Amona Polymer, Polyacrylamide Times, Polyacrylamide, PolyCdiallylmethylmethylmmonium chloride, Polymers, polyimines, starches and mixtures thereof. 11, ICompozit-anyag, mely tartalmaz felületkezelt kalcium-karbonátot és sóz tisztításával és/vagy iszapok és/vagy üledékek vizniemesítésevel nyerhető szemiyeződescket, az eljárás a kővetkező lépéseket tartalmazza: ai szennyeződéseket tartalmazó tisztítandó vizet és/vagy vizmentesltendö Iszapot és/vagy üledéket blztesiteik, bj legalább egy felületkezelt kaleimn-karbonatot biziesihmk, ahol: a kalcium-karfeonái elérhető telületének legalább 1 %-a legalább egy kationos pétimért tartalmazó bevonattal van: fedve, és c) az a) lépés szerinti vizei-es/vagy iszapot és/vagy üledéket a h) lépes szerinti legalább egy felületkezelt kalcium-karbonáttal énmkeztetjük, felületkezelt kalcium-karbonát és szennyeződések kompozlí anyagának előállítására, attól a legalább egy felületkezelt kalcium-karbonát olyan Miletmődosltott kalcium-karbonátot tartalmaz, melyet előzetesen egy további kezelési lépesben kalionos polimerekkel kezeltünk, és áltól a felületmódosítoti kalcium -karbonátot természetes kafeium-karbonáf és/vagy kicsapott kalcium-karbonát sawal és széndioxiddal való reagaltalasa; útján nyertük, a felületkezelt kalcium-karbonát előállítása előtt, aboi a széndioxid in situ képződött a savas kezelés során és/vagy külső forrásból fett betáplálva.11, an ICPC material comprising a surface treated calcium carbonate and a semi-precipitating sludge to be obtained by purification of salt and / or sludge and / or sediment, the method comprising the steps of: a water and / or sludge to be treated with impurities, and / or sludge to be dewatered, bj at least one surface treated kaleimn carbonate, wherein: at least 1% of the available surface area of the calcium carafone has a coating comprising at least one cationic paste: covered, and c) the water / sludge and / or sediment of step a) (ah) self-treated with at least one surface-treated calcium carbonate for the preparation of a surface-treated calcium carbonate and impurity composite material, comprising at least one surface treated calcium carbonate having a Millet-treated calcium carbonate which has been treated in a further treatment step with potassium polymers. from us, and from it, the surface-modified calcium carbonate is a natural caffeum carbonate and / or a precipitated calcium carbonate and carbon dioxide reagent; prior to the preparation of the surface-treated calcium carbonate, the carbon dioxide was formed in situ during the acid treatment and / or fed from the external source. 12,. A II. igénypont szeműi kompozit anyag, aboi az a) lépés szerinti víz és/vagy iszap és/vagy üledék az ipán szennyvizek, ivóvíz, városi szennyvíz, iszap, mini kikötői iszap, fe~ tyano. iszap, tengerparti iszap, vagy emésztett iszap, sörfőzdék vagy italgyárak hulladékvize vagy kezelivize, papíripar, színezék-, festék- vagy bevonóipar hulladékvize vagy kezelővize, mezőgazdasági hulladékvíz, vágébidi hulladékvíz. boripari hulladékvíz és bőreserzö ipar hulladékvíz közül van ki választva. 13. Á 11. vagy 12, igénypont szerinti kompozit anyag, aboi a legalább egy felületkezelt kalcium-karbonát kalcium-karbonát szemeséinek d«( átlagos részecske átmérője 0,01 μ·η és 250 pm közötti énék, előnyösen 0,06 pm és 225 μτη közötti, előnyösebben Ipm és 200 pm, még olönyősebhen. í pm és ISO pm közötti, és legelőnyösebben I por és 100 pm közötti, és/vagy a felületkezelt kalcium-karbonát szemcsék iápagos felülete 1-250 ué/g, még előnyösebben: 20-200 uP/g, még előnyösebben. 30-150 m% és legelőnyösebben 30-1001 ntfeg. 14. A 11-13. igénypernek bámtelyike szerinti kornpozií anyag, aboi a legalább egy felületkezelt kalcium-karbonát bevonata magában foglal legalább egy kahonos polimert, melynek töltés sűrűsége ImEp/g és IS nVEq 'g közötti, előnyösebben 2,5 mBq/g és 1.2,5 mBq/g közötti, és legelőnyösebben 5 nrlBq/g és 10 mEq/g közötti, és/vagy a teiüíetkezdt kaJeinm-kárboúáf bevonat tartalmaz legalább egy kationos polimer!, amelyben a monomer egységek legalább ö0%-a, előnyösen legalább 70%-a, előnyösebben legalább 80%-a, még előnyösebben legalább 90%-a, és legelőnyösebben 100%-a kationos töltéssel rendelkezik. 15. A 11-14 . igénypontok bármelyike szerinti kompozit anyag, ahol a legalább egy felületkezelt kalcium-karbonát bevonata legalább egy kalionos polimert tartalmaz, melynek Μ» átlagos molekulatömege 1 000 000 g/mol alaki, előnyösen 50 ÖOO-750 000 g/mol, még előnyösebben 50 0ÖÖ-6S0 000 g/mol, és legelőnyösebben 100 000 - 300 000 g/mol. lé. A 11 -15. ígéayjpontök bármelyike .szemtt koœpozlt anyag, ahol a legalább egy felületkezelt. kaleimB-karbonét bevonatatartalmaz legalább egy kaikmos polimert, amely a dlallil-dialkil miméniom séki tercier es kvateraizalt aminek; kvaternizâiî Iminek; előnyösen diaitil-dialkil msmémqm abb csoportból kiválasztott monomer egységeken alapuló bomopolimer, 17. A 11-15. igénypontok bármelyike .szerinti kompozit anyagf aboi a legalább egy felületkezelt fcaleient-fcarbonát bevonata tartalmaz legalább egy olyas kationos: polimert, amely a diallil-diaíkil ammonium sók közül választott monomer egységeken, és az aloálamid; metakrilamid; Ν,Ν-dimeti l-akrilamid; atólstv; apáakplsav; vMlszulftmav; vMlpimlidos; Mdroxil~ei.il-akrilát; szurok meüi-metakrilái; vinll-aeetàî és ezek keverékei csoportból válasz-tölt k.omonomer egységeken alapul. I S. A I !~1 Ά igénypontok 'bármelyike szeműi kompozit anyag, aboi a kalcium-karbonát elérhető felületének legalább 10%-a, előnyösen az elérhető felölet legalább 20%-a, előnyösebben legalább 30%-a, még előnyösebben legalább 40%-a, és legelőnyösebben legalább 50%' kationos polimert tartalmazó bevonattal van fedve, 19. A ! I-IS, igénypontok bármelyike szerinti kompozit anyag, aboi a legalább egy Muteikmeli kalcium-karbonát por és/vagy gmnoláten vagy zagy formájában-van, 20. A 11-19, igénypontok bármelyike szerinti kornpoz.it anyag, aha! az eljárás tartalmaz egy további d) lépest, melynek során .az a) lépés szerinti tisztítandó vizet és· vagy a víz-mentesítendő iszapot és/vagy Üledékei legalább egy polimer llokkidáló szer segédanyaggal érintkeztepök. 21. A 20. igénypont szerinti kompozit anyag, aboi a polimer flokknlálő szer segédanyag Mw átlagos molekulatömege lööööö-lö 000 ÖÖG g/tnol, előnyösen. 3®8 000-S 00Ö 9Ö0 g/mol, még előnyösebben 3-ŐÖ ÖÖO-IíKb> ööt) g/mol és legelőnyösebben 300 OOO-8QO 000 g/tnol, és/vagy a flokkuiálé szer segédanyag nem-ionos vagy ionos:, előnyösen kationos vagy anionos polimer, a poliakrilamidok, poliakrilátók, poli(diallil-dlmetil-ammómmn~kloridl:, polktilénirránek, poliammok, keményítők és ezek keverékei közül kiválasztva, ti, A 20. vagy 21. igénypontok bármelyike szerinti kompoz.it anyag, ahol a c) és d); lépés egyidejűleg vagy külön-külön. előnyösen egyidejűleg vart lefolytatva. 23. A 11-22. igénypontok bármelyike szerinti kompoz.it anyag, ahol a e) és/vagy á) lépést az: a) lépés szerinti kszelestdő viz és/vagy iszap és/vagy üledék miliőiének legalább részben: való lefedését legalább egy, b) lépés szerimi felületkezelt kalcium-karbonáttal végez zük. és/vagy az a) lépes szerinti kezelendő vizet. é$/vagy iszapot és/vagy üledéket a jb) lépés szerinti legalább egy felületkezelt kdeittm-teböÄaf ÔssaekeveQiük. 24, : A 1 1 -23, igénypontok bármelyike szerinti kompozlt anyag, altot a e) éslvagy d) lépest egyszer vagy többször megismételjük, 25. A 11-24, Igénypontok bármelyike szerinti kompoztt anyag, ahol a legalább egy felületkezelt kalelnm-karbonát és a szennyeződések által alkotott kompozh anyagot a viz ás/vagy iszap éslvagy üledék fázisból szikessel, elépítéssé és/vagy eentriíngálágssl távolífink el.12 ,. The II. Claims 1. Composite Composite Material, Water and / or Sludge of Step a) and / or Sludge from Industrial Waste Water, Drinking Water, Urban Waste Water, Sludge, Mini Port Sludge, Phenomenon. sludge, coastal sludge or digested sludge, waste water or treatment water from breweries or beverage factories, waste water or treatment water from the paper industry, dye, paint or coating industries, agricultural waste water, waste water from waste mills. Wastewater from waste water and leather industry is selected from waste water. 13. A composite material according to claim 11 or claim 12, wherein said at least one surface treated calcium carbonate has a calcium carbonate grain d '(average particle diameter between 0.01 µ · η and 250 µm, preferably 0.06 µm and 225 µm). µτη, more preferably Ipm to 200 µm, even more than 50 µm, and most preferably I powder to 100 µm, and / or the surface area of the treated calcium carbonate particles is 1 to 250 µg / g, more preferably 20 -200 µP / g, more preferably 30-150 m% and most preferably 30-1001 ntfeg 14. The coating of corn bulb material according to claims 11-13, at least one surface treated calcium carbonate, comprises at least one coon polymer; having a loading density of between ImEp / g and IS nVEq, more preferably between 2.5 mBq / g and 1.2.5 mBq / g, and most preferably between 5 nbBq / g and 10 mEq / g, and / or the milking process. coating contains at least bb is a cationic polymer in which at least 0%, preferably at least 70%, more preferably at least 80%, more preferably at least 90%, and most preferably 100% of the monomeric units have a cationic charge. 15. In Figures 11-14. Composite material according to any one of claims 1 to 5, wherein the coating of the at least one surface-treated calcium carbonate comprises at least one potassium polymer having an average molecular weight of 1 000 000 g / mol, preferably 50 µO-750 000 g / mol, more preferably 50 0Ö-6S0 000 g / mol, and most preferably 100,000 to 300,000 g / mol. juice. The 11 -15. any of the following: material containing at least one surface treatment. kaleimB-carbonate coating comprises at least one atmospheric polymer which is dlallyl dialkyl mimene and tertiary and quaternary fiber; kvaternizâiî Iminek; preferably a bomopolymer based on monomer units selected from the group consisting of diaityl dialkyl msmqmbbb. The at least one surface-treated fc e-carbonate coating of the composite material according to any one of claims 1 to 4, comprises at least one cationic polymer on monomer units selected from diallyl dialyl ammonium salts and alo-amide; methacrylamide; Ν, eti-dimethyl-1-acrylamide; atólstv; apáakplsav; vMlszulftmav; vMlpimlidos; Mdroxil ~ ei.il acrylate; pitch methyl methacrylics; vinyl-aethole and mixtures thereof are based on a group of charge monomer units. Composite material according to any one of Claims 1 to 3, at least 10% of the available surface area of calcium carbonate, preferably at least 20%, more preferably at least 30%, more preferably at least 40% of the available surfactant -a, and most preferably, a coating comprising at least 50% 'cationic polymer; A composite material according to any one of claims I-IS, wherein at least one Muteikmeli calcium carbonate powder and / or gmnolate or slurry is present. the method comprises a further step d) wherein .the water to be purified according to step a) and / or the water-sludge and / or sludge to be watered is contacted with at least one polymer blocking agent. 21. The composite material according to claim 20, wherein the polymer molecular weight diluent excipient Mw has an average molecular weight of about 1000 g / tonne, preferably. 3,000-S-00O 9O0 g / mol, more preferably 3-O-O-Ib)) g / mol and most preferably 300, 000-8O000 g / t, and / or the non-ionic or ionic flocculant excipient: , preferably cationic or anionic polymers, polyacrylamides, polyacrylates, poly (diallyldimethylammonium chloride, polylenedlenes, polyamides, starches and mixtures thereof, i.e., a composite material according to any one of claims 20 or 21, where c) and d); step simultaneously or separately. preferably run simultaneously. 23. The 11-22. Composite material according to any one of claims 1 to 4, wherein ae) and / or step a) are at least partially covered by the milling water and / or sludge and / or sediment of step a) by at least one step b) of surface treated calcium carbonate. do it. and / or the water to be treated according to step a). and / or sludge and / or sediment are at least one surface treated kdeittm teböfafe of step jb). 24, Composite material according to any one of claims 1 to 23, altot ae) and or d) is repeated one or more times, 25. The composite material according to any one of claims 11-24, wherein the at least one surface treated calendula carbonate and dirt-based composite material is removed from the water / sludge and / or sediment phase by scaling, construction, and / or eentrination.
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